Supporting Information (NMR Spectra) Stereoselective synthesis of trans-THF rings using oxidative cyclisation– radical deoxygentaion sequence: Application to the formal synthesis of trans- (2R,5R)-linalool oxide Nadeem S. Sheikh Department of Chemistry, Faculty of Science, King Faisal University P.O. Box 380, Al-Ahsa 31982, Saudi Arabia Email: [email protected]; Fax: +966 (0)13 588 6437; Tel. +966 (0)13 589 9574 Copies of NMR spectra Page Contents S 2 1 H and 13 C NMR spectra for compound 15 S 3 1 H and 13 C NMR spectra for compound (±)-20 S 4 1 H and 13 C NMR spectra for compound 22 S 5 1 H and 13 C NMR spectra for compound 23 + minor diastereoisomer S 6 Expansion of 1 H NMR spectrum for compound 23 + minor diastereoisomer S 7 1 H and 13 C NMR spectra for compound 25 S 8 1 H and 13 C NMR spectra for compound 26 + minor diastereoisomer S 9 Expansion of 1 H NMR spectrum for compound 26 + minor diastereoisomer S 10 1 H and 13 C NMR spectra for compound 27 S 11 Expansion of 1 H NMR spectrum for compound 27 S 12 1 H and 13 C NMR spectra for compound 28 S 13 Expansion of 1 H NMR spectrum for compound 28 S 14 1 H and 13 C NMR spectra for compound 31 S 15 1 H and 13 C NMR spectra for compound (±)-32 S 16 1 H and 13 C NMR spectra for compound (±)-33 S 17 Expansion of 1 H NMR spectrum for compound (±)-33 S 18 1 H and 13 C NMR spectra for compound (±)-34 S 19 Expansion of 1 H NMR spectrum for compound (±)-34 S 20 1 H and 13 C NMR spectra for compound 35 S 21 1 H and 13 C NMR spectra for compound 36 S 22 Expansion of 1 H NMR spectrum for compound 36 S 23 1 H and 13 C NMR spectra for compound 37 S 24 Expansion of 1 H NMR spectrum for compound 37 S 25 1 H and 13 C NMR spectra for compound 38 S 26 Expansion of 1 H NMR spectrum for compound 38 S 27 1 H and 13 C NMR spectra for compound 39 S 28 Expansion of 1 H NMR spectrum for compound 39 Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2014
Welcome message from author
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
Supporting Information (NMR Spectra)
Stereoselective synthesis of trans-THF rings using oxidative cyclisation–
radical deoxygentaion sequence: Application to the formal synthesis of trans-
(2R,5R)-linalool oxide
Nadeem S. Sheikh
Department of Chemistry, Faculty of Science, King Faisal University
P.O. Box 380, Al-Ahsa 31982, Saudi Arabia
Email: [email protected]; Fax: +966 (0)13 588 6437; Tel. +966 (0)13 589 9574
Copies of NMR spectra
Page Contents
S 2 1H and
13C NMR spectra for compound 15
S 3 1H and
13C NMR spectra for compound (±)-20
S 4 1H and
13C NMR spectra for compound 22
S 5 1H and
13C NMR spectra for compound 23 + minor diastereoisomer
S 6 Expansion of 1H NMR spectrum for compound 23 + minor diastereoisomer
S 7 1H and
13C NMR spectra for compound 25
S 8 1H and
13C NMR spectra for compound 26 + minor diastereoisomer
S 9 Expansion of 1H NMR spectrum for compound 26 + minor diastereoisomer
S 10 1H and
13C NMR spectra for compound 27
S 11 Expansion of 1H NMR spectrum for compound 27
S 12 1H and
13C NMR spectra for compound 28
S 13 Expansion of 1H NMR spectrum for compound 28
S 14 1H and
13C NMR spectra for compound 31
S 15 1H and
13C NMR spectra for compound (±)-32
S 16 1H and
13C NMR spectra for compound (±)-33
S 17 Expansion of 1H NMR spectrum for compound (±)-33
S 18 1H and
13C NMR spectra for compound (±)-34
S 19 Expansion of 1H NMR spectrum for compound (±)-34
S 20 1H and
13C NMR spectra for compound 35
S 21 1H and
13C NMR spectra for compound 36
S 22 Expansion of 1H NMR spectrum for compound 36
S 23 1H and
13C NMR spectra for compound 37
S 24 Expansion of 1H NMR spectrum for compound 37
S 25 1H and
13C NMR spectra for compound 38
S 26 Expansion of 1H NMR spectrum for compound 38
S 27 1H and
13C NMR spectra for compound 39
S 28 Expansion of 1H NMR spectrum for compound 39
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2014
S
Supporting Information
2
N-(3-Methyl-2-methylene-propylate)-(2R)-camphor-10,2-sultam (15)
1H NMR (300 MHz, CDCl3) and
13C NMR (75 MHz, CDCl3)
N-(3-Methyl-2-methylene-propylate)-(2R)-camphor-10,2-sultam.esp
Chemical Shift (ppm)9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
2.955.468.122.000.991.97
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.7
05
.70
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
65
.66
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
5.6
55
.65
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
4.0
24
.02
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.5
03
.50
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
3.3
73
.37
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
N-(3-Methyl-2-methylene-propylate)-(2R)-camphor-10,2-sultam.esp
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
17
1.2
51
71
.25
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
13
8.9
81
38
.98
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
12
4.3
11
24
.31
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
65
.48
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
53
.56
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
48
.00
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
47
.70
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
45
.25
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
38
.33
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
21
.30
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
19
.87
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
18
.70
O
15
O2SN
S
Supporting Information
3
Rac. (2S,5R)-Perfluorophenyl tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-2-
carboxylate (20)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
PFP-H.esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
3.853.472.182.071.041.011.060.93
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.9
23
.92
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
52
.35
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.3
32
.33
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
Rac. (2S,5R)-Perfluorophenyl tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-2-carboxylate
Chemical Shift (ppm)200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
17
0.0
11
70
.01
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.97
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
87
.26
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.33
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
71
.60
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
65
.97
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
32
.40
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
27
.42
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.94
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
OH
O
OC6F5
HOOH
(±)-20
S
Supporting Information
4
(S)-3-(6-Methyl-2-methylenehept-5-enoyl)-4-benzyloxazolidin-2-one (22)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(S)-3-(6-Methyl-2-methylenehept-5-enoyl)-4-benzyloxazolidin-2-one.esp
Chemical Shift (ppm)9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
2.553.102.342.311.241.222.401.000.812.451.912.77
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.4
07
.40
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
87
.38
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
67
.36
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
47
.34
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
85
.48
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.4
65
.46
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
95
.19
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
5.1
85
.18
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.3
14
.31
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
94
.29
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
74
.27
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
24
.22
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
4.2
04
.20
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
43
.44
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
33
.43
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
3.4
03
.40
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
82
.88
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
62
.86
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
52
.85
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.8
22
.82
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
82
.48
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.7
31
.73
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
(S)-3-(6-Methyl-2-methylenehept-5-enoyl)-4-benzyloxazolidin-2-one.esp
Chemical Shift (ppm)280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
171
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.01
71
.0
152
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.81
52
.8
143
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.91
43
.9
135
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
35
.11
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
32
.61
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.41
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
29
.01
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
27
.41
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.11
23
.1119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4119
.4
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
66.4
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
55.3
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
37.7
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
33.0
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
26.5
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
25.6
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
O
22N
O
O
Bn
S
Supporting Information
5
(2R,5S)-((S)-4-benzyloxazolidin-2-one)tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-
yl)furan-2-carboxylate (23);
(2S,5R)-((S)-4-benzyloxazolidin-2-one)tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-
2-carboxylate (minor diastereoisomer)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(2S,5R)-((S)-4-benzyloxazolidin-2-one)tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
3.433.153.322.341.431.310.231.000.220.980.390.732.160.995.66
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
(2S,5R)-((S)-4-benzyloxazolidin-2-one)tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
17
3.4
71
73
.47
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
15
2.3
01
52
.30
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
13
5.1
31
35
.13
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
9.4
31
29
.43
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
8.9
41
28
.94
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
12
7.3
51
27
.35
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
90
.23
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
89
.91
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.24
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
87
.05
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
71
.20
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.76
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
66
.55
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.98
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
56
.70
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
37
.75
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.93
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
31
.62
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.51
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
27
.36
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.40
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
26
.21
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.82
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
24
.54
OH
O
NO
HO
23 (major diastereoisomer)
+ minor diastereoisomer
(dr ~4:1)
HO
O
Bn
S
Supporting Information
6
(2S,5R)-((S)-4-benzyloxazolidin-2-one)tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.231.000.220.980.390.732.160.99
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.7
04
.70
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
84
.68
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
74
.67
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
64
.66
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
54
.65
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.6
44
.64
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
64
.26
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
34
.23
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.2
14
.21
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
94
.19
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
74
.17
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
54
.15
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
(2S,5R)-((S)-4-benzyloxazolidin-2-one)tetrahydro-2-(hydroxymethyl)-5-(2-hydroxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3
No
rma
lize
d In
ten
sity
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
3.433.153.322.341.431.31
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
63
.26
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
53
.25
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
33
.23
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
23
.22
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
13
.21
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
3.2
03
.20
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
82
.78
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
52
.75
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.7
22
.72
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
22
.32
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
92
.29
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
1.1
11
.11
S
Supporting Information
7
(1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl 6-methyl-2-methylenehept-5-enoate (25)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl 6-methyl-2-methylenehept-5-enoate.esp
Chemical Shift (ppm)9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
7.013.003.205.742.561.165.200.950.741.020.990.774.03
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
67
.26
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.2
57
.25
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
47
.14
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
25
.72
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.7
15
.71
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
35
.33
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.3
25
.32
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
25
.12
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
15
.11
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
5.1
05
.10
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
41
.64
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.6
21
.62
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
(1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl 6-methyl-2-methylenehept-5-enoate.esp
Chemical Shift (ppm)280 260 240 220 200 180 160 140 120 100 80 60 40 20 0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
181
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.21
81
.2
166
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.31
66
.3
151
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.41
51
.4
140
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.61
40
.6
132
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
32
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
28
.01
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.41
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
25
.01
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
24
.41
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.61
23
.6
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.3
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
77.0
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
76.7
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
74.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
50.6
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
41.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
39.8
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
34.6
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.7
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
31.3
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
26.4
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
25.7
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
21.8
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
17.7
O
25O
Ph
S
Supporting Information
8
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-
(2-hydroxypropan-2-yl)furan-2-carboxylate (26);
(2R,5S)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-(2-
hydroxypropan-2-yl)furan-2-carboxylate (minor diastereoisomer)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
26+SI2.esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
5.963.104.369.514.234.526.692.170.821.072.820.250.961.000.291.125.54
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
26+SI2.esp
Chemical Shift (ppm)216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.5
91
73
.59
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
17
3.0
91
73
.09
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.7
61
50
.76
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
15
0.5
11
50
.51
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
8.0
31
28
.03
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.6
61
25
.66
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.5
81
25
.58
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
12
5.3
41
25
.34
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.66
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
87
.35
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.47
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
86
.06
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
76
.18
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
71
.31
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.96
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
65
.58
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
50
.33
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.59
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
41
.43
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
40
.12
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
34
.51
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
32
.11
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
31
.31
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
28
.75
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
27
.16
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.10
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
26
.04
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
25
.17
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
OH
O
O
26 (major diastereoisomer)
+ minor diastereoisomer
(dr ~3.5:1)
HOPhOH
S
Supporting Information
9
26+SI2.esp
Chemical Shift (ppm)5.10 5.05 5.00 4.95 4.90 4.85 4.80 4.75 4.70 4.65
No
rma
lize
d In
ten
sity
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
1.000.29
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
54
.95
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
44
.94
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
14
.91
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
26+SI2.esp
Chemical Shift (ppm)3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
5.963.104.369.514.234.526.692.170.821.07
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.7
42
.74
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10 2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
91
.59
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
91
.49
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
41
.24
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.1
31
.13
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
71
.07
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
61
.06
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
S
Supporting Information
10
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-
(methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate (27)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-(methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
17.290.963.002.165.864.273.002.071.003.052.170.970.970.971.000.973.77
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-(methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
18
1.2
61
81
.26
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51 1
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
51
50
.85
15
0.8
5
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
7.9
51
27
.95
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.7
31
25
.73
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
12
5.2
21
25
.22
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.80
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
87
.58
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.327
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
7.0
07
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
6.6
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
5.8
87
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
97
4.9
9
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
66
.73
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
50
.40
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
41
.60
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59
34
.59 31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49
31
.49 3
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
93
1.2
92
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.9
32
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
42
7.3
4 21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
2.5
82
.58
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
-0.4
8-0
.48
OH
O
O
27
TMSOPhOTMS
S
Supporting Information
11
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-(methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6
No
rma
lize
d In
ten
sity
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.970.970.971.00
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
4.0
04
.00
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
93
.99
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
3.5
63
.56
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-(methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
17.290.963.002.165.864.273.002.071.003.052.17
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.8
01
.80
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
41
.54
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
41
.34
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.3
01
.30
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
S
Supporting Information
12
(2R,5S)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-
(methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate (28)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(2R,5S)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2- (methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
17.481.093.142.135.913.175.125.171.191.990.961.000.983.74
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
(2R,5S)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2- (methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
-0.05
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
18
1.1
51
81
.15
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
17
2.7
91
72
.79
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
15
0.4
11
50
.41
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
7.9
41
27
.94
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.9
31
25
.93
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
12
5.2
81
25
.28
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.75
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
87
.55
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
75
.98
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
74
.92
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
66
.38
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
50
.60
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
41
.63
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
40
.52
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
34
.55
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
31
.25
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
30
.73
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.83
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
27
.50
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
25
.42
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
23
.34
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
21
.74
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
-0.5
5-0
.55
OH
O
O
TMSOPhOTMS
28
S
Supporting Information
13 (2R,5S)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2- (methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8
No
rma
lize
d In
ten
sity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
1.990.961.00
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
94
.89
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
64
.86
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.9
03
.90
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
93
.89
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.8
83
.88
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
73
.77
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
(2R,5S)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2- (methoxytrimethylsilyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3
No
rma
lize
d In
ten
sity
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
17.481.093.142.135.913.175.125.171.19
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
82
.18
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
52
.15
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
11
.51
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.5
01
.50
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.9
20
.92
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
90
.89
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
50
.75
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.7
20
.72
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.6
90
.69
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
S
Supporting Information
14
N-[O-((2S,5R)-2-Methyl O-phenylcarbonothioatyl) tetrahydro-5-(2-hydroxypropan-2-yl)furan-2-yl]-
2-(2R)-camphor-10,2-sultam (31)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
N-[O-((2S,5R)-2-Methyl O-phenylcarbonothioatyl) tetrahydro-5-(2-hydroxypropan-2-yl)furan-2-yl]-2-(2R)-camphor-10,2-sultam .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
3.139.382.246.221.101.051.020.652.121.911.001.001.410.901.62
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
37
.13
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
5.0
05
.00
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.9
74
.97
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
84
.18
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
14
.11
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
4.0
94
.09
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
73
.57
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.5
43
.54
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
3.4
73
.47
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.8
42
.84
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.4
42
.44
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.3
02
.30
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
N-[O-((2S,5R)-2-Methyl O-phenylcarbonothioatyl) tetrahydro-5-(2-hydroxypropan-2-yl)furan-2-yl]-2-(2R)-camphor-10,2-sultam .esp
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
19
5.0
81
95
.08
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
17
5.2
81
75
.28
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
15
3.5
11
53
.51
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
9.4
81
29
.48
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
6.5
51
26
.55
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
12
1.9
41
21
.94
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
88
.90
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
87
.47
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
76
.69
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
75
.44
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
71
.30
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
67
.63
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
54
.60
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.93
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
47
.59
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
45
.49
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
39
.25
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
35
.31
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
33
.70
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
27
.32
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
26
.17
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
25
.99
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
24
.00
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
21
.78
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
19
.92
OH
O
O2SN
O31
PhO S
HO
S
Supporting Information
15
Rac. O-((2S,5R)-2-(Methoxycarbonyl) tetrahydro-5-(2-hydroxypropan-2-yl)furan-2-yl)methyl O-
phenyl carbonothioate (32)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
Rac. O-((2S,5R)-2-(Methoxycarbonyl) tetrahydro-5-(2-hydroxypropan-2-yl)furan-2-yl)methyl O-phenyl carbonothioate
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
3.173.202.383.253.000.972.331.520.811.74
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.1
71
.17
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.3
11
.31
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.1
92
.19
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
3.8
03
.80
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
24
.12
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
44
.14
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.1
64
.16
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
07
.10
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.1
27
.12
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.3
97
.39
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
17
.41
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
7.4
37
.43
Rac. O-((2S,5R)-2-(Methoxycarbonyl) tetrahydro-5-(2-hydroxypropan-2-yl)furan-2-yl)methyl O-phenyl carbonothioate
Chemical Shift (ppm)216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
19
4.9
71
94
.97
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
17
2.7
31
72
.73
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
15
3.3
01
53
.30
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
9.4
51
29
.45
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
6.5
41
26
.54
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
12
1.7
51
21
.75
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
88
.23
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
84
.53
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.31
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
75
.29
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
71
.03
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
52
.56
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
32
.83
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
25
.60
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
24
.65
OH
(±)-32O
OMe
O
S OPh
HO
S
Supporting Information
16
Rac. (2S,5R)-Methyl tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-2-yl)furan-2-carboxylate
(33)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
Rac. (2S,5R)-Methyl tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-2-yl)furan-2-carboxylate
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
6.373.013.001.062.081.030.743.811.030.80
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
0.1
50
.15
Rac. (2S,5R)-Methyl tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-2-yl)furan-2-carboxylate
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
17
4.4
61
74
.46
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
88
.56
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
86
.81
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
75
.18
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
66
.14
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
52
.17
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
32
.42
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
27
.37
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.98
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
26
.31
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
OH
(±)-33 OH
OMe
O
TMSO
S
Supporting Information
17 Rac. (2S,5R)-Methyl tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-2-yl)furan-2-carboxylate
Chemical Shift (ppm)4.05 4.00 3.95 3.90 3.85 3.80 3.75 3.70
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
3.811.030.80
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
73
.97
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
43
.84
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
23
.82
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
43
.74
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.7
13
.71
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
3.6
93
.69
Rac. (2S,5R)-Methyl tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-2-yl)furan-2-carboxylate
Chemical Shift (ppm)3.05 3.00 2.95 2.90 2.85 2.80 2.75 2.70 2.65 2.60 2.55 2.50 2.45 2.40 2.35 2.30 2.25 2.20 2.15 2.10 2.05 2.00 1.95
No
rma
lize
d In
ten
sity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
1.062.081.030.74
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
12
.91
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
11
.91
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
S
Supporting Information
18
Rac.(2S,5R)-Methyl tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxy-2-yl)
furan-2-carboxylate (34)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
Rac.(2S,5R)-Methyl tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxy-2-yl) furan-2-carboxylate
Chemical Shift (ppm)9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
6.373.002.822.940.942.170.790.950.910.670.510.66
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
8.3
08
.30
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.5
97
.59
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
7.0
37
.03
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.2
71
.27
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
Rac.(2S,5R)-Methyl tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxy-2-yl) furan-2-carboxylate
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
18
3.6
91
83
.69
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
17
3.0
11
73
.01
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
6.8
61
36
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
13
0.8
61
30
.86
11
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
811
7.8
8
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
89
.14
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
84
.76
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
75
.84
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
74
.80
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
52
.68
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
33
.13
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
27
.26
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
25
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
2.4
72
.47
OH
(±)-34
OMe
O
TMSOO
S N N
S
Supporting Information
19
Rac.(2S,5R)-Methyl tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxy-2-yl) furan-2-carboxylate
Chemical Shift (ppm)5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6
No
rma
lize
d In
ten
sity
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
2.170.790.950.91
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
24
.92
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.9
04
.90
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
54
.75
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.7
24
.72
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
64
.06
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
Rac.(2S,5R)-Methyl tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxy-2-yl) furan-2-carboxylate
Chemical Shift (ppm)2.35 2.30 2.25 2.20 2.15 2.10 2.05 2.00 1.95
No
rma
lize
d In
ten
sity
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
2.940.94
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
72
.27
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
62
.26
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
52
.25
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
42
.24
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
32
.23
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
22
.22
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
12
.21
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.2
02
.20
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
62
.06
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
S
Supporting Information
20
N-[(2S,5R)-Tetrahydro-5-(2-hydroxypropan-2-yl)-2-methylfuranoyl]-2-(2R)-camphor-10,2-sultam
(35)
1H NMR (300 MHz, CDCl3) and
13C NMR (75 MHz, CDCl3)
N-[(2S,5R)-Tetrahydro-5-(2-hydroxypropan-2-yl)-2-methylfuranoyl]-2-(2R)-camphor-10,2-sultam .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
2.888.393.152.525.433.060.960.831.000.942.15
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.1
04
.10
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
44
.04
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
34
.03
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
4.0
14
.01
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.4
23
.42
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
3.3
83
.38
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.7
62
.76
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.2
82
.28
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
71
.77
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.7
51
.75
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.3
21
.32
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
51
.25
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
1.1
51
.15
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
N-[(2S,5R)-Tetrahydro-5-(2-hydroxypropan-2-yl)-2-methylfuranoyl]-2-(2R)-camphor-10,2-sultam .esp
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
-0.05
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
17
8.4
51
78
.45
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
87
.77
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
85
.98
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.41
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
71
.18
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
67
.67
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
54
.58
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.79
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
47
.46
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
45
.57
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.46
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
39
.33
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
33
.81
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.79
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
26
.12
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
25
.85
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
24
.45
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
23
.49
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
21
.87
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
19
.89
OH
O
O2SN
35
HO
S
Supporting Information
21
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-(2-
trimethylsiloxy-propan-2-yl)furan-2-carboxylate (36)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
9.006.2812.762.974.670.940.931.010.950.950.950.994.32
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
17
.21
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.2
07
.20
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
17
3.5
11
73
.51
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
15
0.3
91
50
.39
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
8.0
21
28
.02
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.6
91
25
.69
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
12
5.3
61
25
.36
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
88
.59
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
86
.13
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.42
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
76
.58
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.92
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
75
.04
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
65
.92
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
50
.42
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
40
.18
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
34
.53
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
32
.55
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
31
.27
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
29
.32
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.38
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.23
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
27
.07
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
26
.45
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
24
.93
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
21
.72
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
2.3
42
.34
OH
O
O
36
TMSOPhOH
S
Supporting Information
22
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0
No
rma
lize
d In
ten
sity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.931.010.950.950.95
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
4.7
34
.73
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
83
.98
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
63
.96
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.9
43
.94
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
33
.73
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
23
.72
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.7
03
.70
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.6
83
.68
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
83
.58
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
53
.55
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
3.5
13
.51
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
32
.93
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
22
.92
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.9
02
.90
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
2.8
92
.89
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(hydroxymethyl)-5-(2-trimethylsiloxy-propan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
9.006.2812.762.974.670.94
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
62
.16
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
32
.13
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
12
.11
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.9
01
.90
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.8
81
.88
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
81
.58
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
71
.57
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
11
.41
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.3
51
.35
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.2
81
.28
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.1
91
.19
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
50
.95
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.9
10
.91
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
70
.87
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
40
.84
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
0.1
60
.16
S
Supporting Information
23
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-(O-methoxy-1H-
imidazol-1-carbothioyl)-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate (37)
1H NMR (300 MHz, CDCl3) and
13C NMR (75 MHz, CDCl3)
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
8.333.412.699.202.962.894.032.010.980.990.981.000.920.974.250.930.88
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
8.3
38
.33
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.6
07
.60
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
17
.31
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
87
.28
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.1
67
.16
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
7.0
17
.01
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)240 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
-0.05
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
18
3.7
81
83
.78
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
17
1.8
91
71
.89
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
15
0.8
41
50
.84
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
7.0
01
37
.00
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
13
0.7
11
30
.71
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
8.1
41
28
.14
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.4
51
25
.45
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
12
5.3
11
25
.31
11
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
311
7.7
3
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
89
.17
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
84
.44
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
75
.86
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
74
.63
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
49
.87
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
41
.41
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
39
.98
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
34
.33
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
32
.76
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
31
.16
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
27
.40
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
26
.99
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.98
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
25
.59
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
21
.52
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
2.4
62
.46
OH
O
O
37
TMSOPhO
S N N
S
Supporting Information
24
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)5.05 5.00 4.95 4.90 4.85 4.80 4.75 4.70 4.65 4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25 4.20 4.15 4.10 4.05 4.00
No
rma
lize
d In
ten
sity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.980.990.981.00
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
84
.88
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
74
.87
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
54
.85
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
44
.84
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
34
.83
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
44
.74
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.7
14
.71
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
24
.42
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.4
04
.40
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
84
.08
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
74
.07
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
4.0
54
.05
(2S,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl) tetrahydro-2-(O-methoxy-1H-imidazol-1-carbothioyl)-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
8.333.412.699.202.962.894.032.01
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
81
.48
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
71
.47
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
41
.44
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
31
.43
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.4
21
.42
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.3
71
.37
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
31
.23
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.1
81
.18
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
1.0
11
.01
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
80
.98
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
10
.81
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
80
.78
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
0.1
00
.10
S
Supporting Information
25
(2R,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-methyl-5-(2-
trimethylsiloxypropan-2-yl)furan-2-carboxylate (38)
1H NMR (400 MHz, CDCl3) and
13C NMR (100 MHz, CDCl3)
(2R,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-methyl-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
9.006.456.452.646.274.115.200.951.001.024.29
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
27
.32
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.3
07
.30
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
97
.29
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
97
.19
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
87
.18
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
7.1
77
.17
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
0.1
30
.13
(2R,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-methyl-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20
No
rma
lize
d In
ten
sity
-0.05
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
17
5.1
11
75
.11
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
15
0.5
91
50
.59
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
7.9
81
27
.98
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.7
11
25
.71
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
12
5.2
91
25
.29
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
87
.45
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
83
.96
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.32
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
77
.00
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
76
.68
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
75
.63
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
74
.78
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
50
.41
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
41
.52
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
40
.27
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
36
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
34
.56
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
31
.29
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
29
.64
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.87
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
27
.31
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
26
.11
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
25
.28
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
24
.53
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
23
.96
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
21
.76
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
2.5
72
.57
OH
O
O
38
TMSOPh
S
Supporting Information
26 (2R,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-methyl-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6
No
rma
lize
d In
ten
sity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.951.00
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
24
.82
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
14
.81
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.8
04
.80
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
84
.78
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
74
.77
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
4.7
64
.76
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
53
.95
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
33
.93
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
3.9
13
.91
(2R,5R)-((1R,2S,5R)-5-Methyl-2-(2-phenylpropan-2-yl)cyclohexyl)tetrahydro-2-methyl-5-(2-trimethylsiloxypropan-2-yl)furan-2-carboxylate .esp
Chemical Shift (ppm)2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8
No
rma
lize
d In
ten
sity
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
0.070
0.075
0.080
6.456.452.646.274.115.20
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
42
.04
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
32
.03
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
22
.02
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
12
.01
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
91
.89
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
71
.87
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
51
.85
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
31
.63
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.6
11
.61
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
61
.56
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
51
.55
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
31
.53
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.5
21
.52
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
61
.46
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
51
.45
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.4
01
.40
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
91
.39
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
81
.38
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.3
61
.36
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
21
.22
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.2
11
.21
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
51
.05
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
41
.04
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
31
.03
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
21
.02
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
1.0
01
.00
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
90
.99
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
70
.97
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
60
.96
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
40
.94
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
30
.93
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.9
00
.90
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
60
.86
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
50
.85
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
30
.83
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
20
.82
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.8
00
.80
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
90
.79
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
70
.77
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
60
.76
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
40
.74
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
0.7
30
.73
S
Supporting Information
27
(2R,5R)-Tetrahydro-2-methyl-5-(2-trimethylsilyl-oxy-propan-2-yl)furan-2-carbaldehyde (39)
1H NMR (400 MHz, CDCl3) and
13C DEPT135 NMR (100 MHz, CDCl3)
(2R,5R)-Tetrahydro-2-methyl-5-(2-trimethylsilyl-oxy-propan-2-yl)furan-2-carbaldehyde .esp
Chemical Shift (ppm)12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
No
rma
lize
d In
ten
sity
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
8.633.393.203.001.011.051.010.990.940.74
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
9.5
89
.58
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
7.2
77
.27
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
0.1
20
.12
(2R,5R)-Tetrahydro-2-methyl-5-(2-trimethylsilyl-oxy-propan-2-yl)furan-2-carbaldehyde -D 135.esp
Chemical Shift (ppm)240 220 200 180 160 140 120 100 80 60 40 20
No
rma
lize
d In
ten
sity
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
20
4.0
62
04
.06
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
88
.60
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
33
.27
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
27
.92
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.58
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
26
.18
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
21
.32
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
2.9
52
.95
OH
O
H
39
TMSO
S
Supporting Information
28 (2R,5R)-Tetrahydro-2-methyl-5-(2-trimethylsilyl-oxy-propan-2-yl)furan-2-carbaldehyde .esp
Chemical Shift (ppm)3.90 3.89 3.88 3.87 3.86 3.85 3.84 3.83 3.82 3.81 3.80 3.79 3.78 3.77 3.76 3.75 3.74 3.73
No
rma
lize
d In
ten
sity
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.94
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
33
.83
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.8
13
.81
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
3.7
93
.79
(2R,5R)-Tetrahydro-2-methyl-5-(2-trimethylsilyl-oxy-propan-2-yl)furan-2-carbaldehyde .esp
Chemical Shift (ppm)2.15 2.10 2.05 2.00 1.95 1.90 1.85 1.80 1.75 1.70 1.65 1.60 1.55 1.50 1.45 1.40 1.35 1.30 1.25
No
rma
lize
d In
ten
sity
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
3.393.203.001.011.051.010.99
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
22
.12
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.1
02
.10
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
92
.09
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
82
.08
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
72
.07
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
52
.05
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
2.0
02
.00
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
91
.99
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
81
.98
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
71
.97
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
61
.96
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
51
.95
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
41
.94
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
31
.93
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.9
21
.92
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
61
.86
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
41
.84
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
31
.83
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
21
.82
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.8
11
.81
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
91
.79
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
81
.78
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
21
.72
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.7
01
.70
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
91
.69
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
81
.68
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
71
.67
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
61
.66
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.6
51
.65
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
91
.29
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
61
.26
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
1.2
01
.20
Related Documents
