Page 1
1
Supporting Information
Highly Enantioselective Synthesis of Syn-Aldols of Cyclohexanones
via Chiral Primary Amine Catalyzed Asymmetric Transfer Aldol
Reactions in Ionic Liquid
Pengxin Zhou, Sanzhong Luo*, Jin-Pei Cheng*
Department of Chemistry, State Key Laboratory of elemento-organic Chemistry, Nankai University,
Tianjin, 300071; China and Beijing National Laboratory for Molecule Sciences (BNLMS), CAS Key
Laboratory for Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of
Sciences, Beijing, 100190 China
[email protected]
Page 2
2
NMR spectra for all the aldol products
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 0.5 ppm
1.
63
31
.6
49
1.
65
91
.6
83
1.
69
21
.7
02
1.
72
41
.7
35
1.
76
31
.7
76
1.
78
21
.7
91
1.
79
61
.8
05
1.
81
81
.8
26
1.
83
31
.8
73
1.
87
72
.0
37
2.
04
62
.0
56
2.
06
52
.0
77
2.
08
92
.0
99
2.
10
92
.3
46
2.
36
62
.3
90
2.
40
82
.4
19
2.
43
02
.4
63
2.
52
82
.5
36
2.
54
72
.5
55
2.
56
82
.5
77
2.
58
72
.5
96
2.
98
62
.9
97
3.
79
95
.3
12
5.
32
25
.3
31
6.
85
96
.8
88
7.
20
67
.2
34
7.
26
2
5.
31
1.
06
2.
09
1.
01
1.
00
3.
07
1.
03
2.
06
2.
01
200 180 160 140 120 100 80 60 40 20 ppm
24.89
26.18
27.99
42.69
55.25
57.28
70.39
76.61
77.03
77.46
113.56
126.92
133.61
158.60
214.91
O OH
OMe2a
O OH
OMe2a
Page 3
3
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 0.5 ppm
-0
.0
16
1.
48
71
.5
18
1.
53
01
.5
41
1.
55
71
.5
72
1.
57
91
.5
85
1.
59
51
.6
04
1.
61
51
.6
26
1.
63
91
.6
55
1.
66
71
.6
83
1.
69
81
.7
09
1.
74
01
.7
52
1.
83
11
.8
69
1.
87
42
.0
70
2.
08
02
.0
90
2.
11
32
.1
23
2.
13
32
.3
73
2.
39
32
.4
18
2.
43
72
.4
43
2.
45
22
.4
58
2.
46
42
.4
73
2.
58
52
.5
90
2.
60
32
.6
09
2.
62
62
.6
32
3.
14
83
.1
59
5.
47
27
.2
48
7.
46
07
.4
89
8.
17
88
.2
07
4.
47
1.
10
1.
03
2.
07
1.
01
0.
99
1.
00
2.
00
1.
97
200 180 160 140 120 100 80 60 40 20 0 ppm
24.76
25.90
27.83
42.59
56.78
70.11
76.60
77.03
77.45
123.44
126.61
147.04
149.11
214.01
O OH
NO2
2b
O OH
NO2
2b
Page 4
4
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 0.5 ppm
-0
.0
12
1.
51
41
.5
26
1.
62
11
.6
37
1.
64
81
.6
83
1.
69
41
.7
08
1.
72
11
.7
32
1.
75
11
.7
61
1.
80
01
.8
12
1.
85
01
.8
55
2.
03
62
.0
45
2.
05
42
.0
62
2.
08
82
.3
43
2.
36
32
.3
86
2.
38
82
.4
06
2.
41
52
.4
21
2.
42
62
.4
31
2.
43
62
.5
51
2.
55
72
.5
84
2.
61
12
.6
17
3.
01
13
.0
22
5.
36
85
.3
77
5.
38
67
.2
30
7.
24
57
.2
53
7.
25
87
.2
73
7.
29
57
.3
02
7.
31
37
.3
23
7.
32
67
.3
51
1.
16
3.
08
1.
03
1.
04
2.
08
1.
02
0.
98
1.
00
5.
10
200 180 160 140 120 100 80 60 40 20 ppm
24.88
26.01
27.95
42.68
57.20
70.61
76.61
77.04
77.46
125.76
126.97
128.16
141.50
214.77
O OH
2c
O OH
2c
Page 5
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 0.5 ppm
1.
48
41
.5
25
1.
53
71
.5
67
1.
63
11
.6
46
1.
65
81
.6
73
1.
68
91
.7
00
1.
72
91
.7
42
1.
75
51
.7
65
1.
77
91
.7
89
1.
80
01
.8
11
1.
81
91
.8
51
1.
85
61
.8
62
1.
86
62
.0
42
2.
05
22
.0
61
2.
07
42
.0
85
2.
09
52
.1
05
2.
33
52
.4
11
2.
41
72
.4
23
2.
42
82
.4
33
2.
43
82
.4
67
2.
54
32
.5
49
2.
56
42
.5
70
2.
58
22
.5
89
2.
60
32
.6
09
2.
98
85
.3
47
7.
12
77
.1
54
7.
17
67
.2
04
7.
25
8
5.
94
1.
16
3.
11
2.
19
1.
08
1.
01
0.
02
0.
03
1.
00
4.
28
200 180 160 140 120 100 80 60 40 20 ppm
21.08
24.89
26.10
27.96
42.68
57.25
70.55
76.61
77.04
77.46
125.70
128.84
136.54
138.51
214.85
O OH
2dCH3
O OH
2dCH3
Page 6
6
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 0.5 ppm
0.
00
11
.3
14
1.
49
81
.5
26
1.
53
91
.6
38
1.
64
91
.6
54
1.
66
51
.6
76
1.
68
01
.6
93
1.
70
71
.7
19
1.
74
91
.7
61
1.
78
91
.8
00
1.
81
31
.8
21
1.
83
21
.8
59
1.
86
61
.8
71
2.
04
82
.0
57
2.
06
72
.0
78
2.
09
02
.1
00
2.
35
12
.3
71
2.
39
52
.4
14
2.
42
92
.4
39
2.
56
32
.5
68
2.
58
22
.5
88
2.
60
42
.6
09
2.
62
12
.9
59
2.
96
65
.3
48
5.
35
75
.3
66
7.
21
37
.2
40
7.
25
97
.3
40
7.
36
8
9.
00
5.
14
1.
05
2.
09
1.
01
0.
97
0.
98
1.
95
1.
99
200 180 160 140 120 100 80 60 40 20 ppm
24.90
26.11
27.98
31.39
34.47
42.70
57.15
70.49
76.62
77.05
77.47
125.05
125.49
138.48
149.82
214.85
O OH
2e
O OH
2e
Page 7
7
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 0.5 ppm
-0
.1
55
-0
.1
36
-0
.1
25
-0
.1
14
-0
.0
83
-0
.0
75
-0
.0
63
-0
.0
53
-0
.0
40
-0
.0
29
-0
.0
18
-0
.0
09
-0
.0
00
0.
01
00
.0
27
0.
04
00
.0
50
0.
08
20
.0
92
0.
13
50
.1
63
0.
20
40
.3
96
0.
40
50
.4
14
0.
43
80
.4
48
0.
45
70
.7
07
0.
72
70
.7
50
0.
76
80
.8
11
0.
82
10
.9
45
0.
95
20
.9
64
0.
97
10
.9
85
0.
99
31
.0
05
1.
01
11
.5
85
3.
79
35
.5
95
5.
80
45
.8
30
5.
85
65
.9
71
5.
99
66
.4
07
6.
43
46
.5
00
5.
46
1.
05
2.
06
1.
03
1.
00
0.
00
1.
00
-0
.0
0-
0.
00
1.
02
1.
02
0.
99
1.
01
200 180 160 140 120 100 80 60 40 20 ppm
23.22
24.39
26.32
41.06
55.24
68.38
75.13
75.55
75.98
119.37
120.54
127.62
130.47
142.42
146.80
212.52
O OH
2fNO2
O OH
2fNO2
Page 8
8
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 0.5 ppm
-0
.0
00
1.
55
51
.5
97
1.
63
01
.6
39
1.
64
51
.6
56
1.
66
41
.6
72
1.
68
31
.6
95
1.
72
41
.7
34
1.
77
61
.8
17
1.
82
92
.0
71
2.
08
12
.3
79
2.
38
12
.3
98
2.
40
12
.4
23
2.
43
92
.4
51
2.
45
53
.1
86
3.
19
75
.6
63
6.
96
56
.9
69
6.
99
16
.9
96
7.
00
07
.0
04
7.
02
77
.0
31
7.
12
97
.1
50
7.
15
47
.1
75
7.
17
97
.2
08
7.
22
67
.2
33
7.
24
57
.2
51
7.
26
37
.5
02
7.
50
77
.5
27
7.
53
27
.5
52
5.
39
1.
04
2.
09
1.
00
0.
97
0.
99
1.
01
1.
03
1.
00
1.
00
200 180 160 140 120 100 80 60 40 20 ppm
24.85
26.23
27.96
42.64
55.01
65.30
65.32
76.60
77.03
77.45
114.72
115.01
123.94
123.99
128.20
128.26
128.33
128.44
157.32
214.77
O OH
2g
F
O OH
2g
F
Page 9
9
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 0.5 ppm
1.614
1.674
1.682
1.698
1.708
1.727
1.739
1.824
1.832
1.872
1.877
2.066
2.075
2.091
2.101
2.110
2.117
2.308
2.329
2.353
2.374
2.397
2.418
2.434
2.439
2.464
2.469
2.478
2.523
2.531
2.557
2.583
2.591
3.054
3.065
5.342
5.351
5.360
7.222
7.250
7.262
7.293
7.321
4.39
1.03
1.03
2.07
1.02
0.99
1.00
4.23
200 180 160 140 120 100 80 60 40 20 ppm
24.84
25.97
27.91
42.64
57.03
70.13
76.59
77.01
77.43
127.17
128.31
132.68
140.00
214.52
O OH
2hCl
O OH
2hCl
Page 10
10
8 7 6 5 4 3 2 1 0 ppm
1.
52
81
.5
34
1.
55
11
.5
74
1.
58
41
.5
89
1.
59
61
.6
13
1.
63
61
.6
49
1.
66
31
.6
75
1.
69
41
.7
03
1.
71
71
.8
13
1.
82
91
.8
46
1.
85
12
.0
45
2.
06
82
.0
77
2.
08
72
.0
98
2.
11
02
.1
21
2.
13
02
.2
82
2.
32
72
.3
46
2.
37
12
.3
89
2.
44
72
.4
93
2.
58
02
.6
04
2.
62
32
.6
42
4.
03
84
.0
52
5.
26
55
.2
78
5.
29
25
.3
05
7.
26
47
.2
72
7.
27
97
.3
01
7.
30
77
.3
48
7.
35
57
.4
82
7.
51
0
4.
58
1.
03
1.
12
1.
06
1.
03
1.
00
1.
00
0.
99
1.
24
0.
94
1.
00
200 180 160 140 120 100 80 60 40 20 ppm
24.90
27.75
30.37
42.71
57.51
70.13
76.60
77.02
77.45
127.62
128.91
129.26
133.52
133.80
137.83
215.06
O OH
2iCl
Cl
O OH
2iCl
Cl
Page 11
11
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 0.5 ppm
-0
.0
00
1.
45
21
.4
66
1.
47
71
.4
94
1.
50
71
.5
19
1.
53
81
.5
48
1.
56
01
.5
77
1.
61
91
.6
45
1.
66
01
.6
73
1.
69
01
.7
03
1.
71
71
.7
28
1.
75
31
.7
64
1.
79
91
.8
39
2.
05
72
.0
64
2.
07
42
.0
99
2.
10
92
.3
40
2.
38
42
.4
04
2.
42
82
.4
48
2.
46
12
.5
06
2.
67
72
.7
06
2.
73
33
.1
48
3.
15
95
.5
66
7.
25
67
.3
44
7.
37
37
.3
76
7.
42
77
.4
50
7.
46
37
.4
75
7.
49
87
.7
98
7.
80
77
.8
25
1.
26
4.
25
1.
03
2.
06
1.
00
0.
99
1.
00
1.
02
1.
99
3.
99
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
24.88
26.07
27.98
42.72
57.10
70.72
76.60
77.02
77.44
123.89
124.53
125.66
126.09
127.63
127.83
127.95
132.62
133.25
138.86
214.87
O OH
2j
O OH
2j
Page 12
12
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 0.5 ppm
-0
.0
05
1.
51
51
.5
22
1.
53
41
.5
46
1.
55
51
.5
75
1.
58
41
.6
24
1.
63
51
.6
41
1.
65
11
.6
64
1.
68
41
.6
94
1.
70
41
.7
18
1.
72
51
.7
47
1.
75
71
.8
04
1.
81
51
.8
25
1.
84
71
.8
57
2.
04
02
.0
62
2.
07
92
.3
54
2.
37
32
.3
93
2.
40
92
.6
76
2.
68
32
.7
09
2.
73
62
.7
43
3.
05
93
.0
71
3.
76
43
.7
95
5.
53
05
.5
40
5.
55
06
.4
18
6.
42
66
.4
77
6.
48
56
.5
05
6.
51
37
.2
60
7.
31
87
.3
46
4.
32
1.
04
1.
07
2.
05
1.
01
0.
99
3.
02
3.
02
1.
00
1.
00
1.
02
1.
00
200 180 160 140 120 100 80 60 40 20 ppm
24.89
26.45
28.07
42.73
54.57
55.24
55.34
65.94
76.62
77.04
77.47
98.20
103.81
121.96
127.98
156.36
159.76
215.51
O OH
2k
OMe
OMe
O OH
2k
OMe
OMe
Page 13
13
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 0.5 ppm
1.
63
41
.6
50
1.
66
71
.6
78
1.
69
41
.7
09
1.
72
01
.7
67
1.
77
61
.7
86
1.
83
01
.8
75
1.
87
92
.0
53
2.
06
22
.0
86
2.
09
62
.2
97
2.
31
82
.3
42
2.
36
22
.3
85
2.
40
32
.4
13
2.
44
82
.4
58
2.
50
72
.5
17
2.
52
62
.5
48
2.
55
82
.9
93
3.
00
2
5.
27
6
5.
93
2
6.
74
96
.7
56
6.
81
5
7.
25
77
.2
63
5.
24
1.
06
3.
13
0.
97
1.
00
2.
03
1.
98
1.
02
200 180 160 140 120 100 80 60 40 20 ppm
24.87
26.15
27.97
42.67
57.32
70.50
76.61
77.03
77.45
100.91
106.59
107.98
118.84
135.54
146.42
147.55
214.80
O OH
2lO
O
O OH
2lO
O
Page 14
14
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 0.5 ppm
-0
.0
00
1.
56
01
.6
65
1.
67
01
.6
81
1.
70
81
.7
35
1.
74
61
.7
75
1.
78
71
.7
95
1.
81
01
.8
15
1.
82
51
.8
38
1.
84
92
.0
76
2.
08
52
.3
76
2.
39
62
.3
98
2.
42
12
.4
37
2.
44
02
.4
46
2.
45
12
.4
57
2.
46
22
.4
67
2.
63
73
.0
22
3.
03
35
.4
23
5.
43
25
.4
41
7.
25
67
.3
08
7.
33
27
.3
39
7.
36
17
.3
88
7.
40
67
.4
26
7.
43
17
.4
49
7.
45
57
.5
57
7.
56
37
.5
78
7.
58
47
.5
94
7.
60
17
.6
06
4.
33
1.
02
2.
04
1.
01
0.
99
1.
00
5.
04
4.
01
200 180 160 140 120 100 80 60 40 20 ppm
24
.9
22
6.
12
27
.9
6
42
.7
0
57
.1
8
70
.5
27
6.
58
77
.0
07
7.
43
12
6.
21
12
6.
90
12
7.
04
12
7.
20
12
8.
74
13
9.
91
14
0.
58
14
0.
89
21
4.
72
O OH
Ph2m
O OH
Ph2m
Page 15
15
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 0.5 ppm
-0
.0
00
1.
53
21
.6
82
1.
69
51
.7
13
1.
72
51
.7
38
1.
75
31
.7
81
1.
79
31
.8
35
1.
85
61
.8
67
1.
90
12
.0
29
2.
04
02
.3
30
2.
35
02
.3
74
2.
45
22
.4
63
2.
47
42
.5
09
2.
76
32
.7
81
2.
80
22
.8
18
2.
83
22
.8
53
2.
97
82
.9
90
3.
00
73
.0
30
3.
04
63
.7
62
3.
77
93
.7
90
3.
80
64
.4
49
4.
46
25
.6
66
5.
67
65
.6
87
7.
15
77
.1
80
7.
20
57
.2
32
7.
24
87
.2
53
7.
26
87
.2
74
7.
36
87
.3
93
1.
08
4.
31
1.
06
1.
05
1.
05
3.
09
2.
07
4.
10
1.
01
1.
00
3.
27
1.
02
200 180 160 140 120 100 80 60 40 20 ppm
24.76
26.38
27.61
42.53
53.63
56.31
67.53
68.40
76.62
77.04
77.47
122.04
125.55
127.68
127.90
137.50
149.60
213.82
O OH2n N
O
O OH2n N
O
Page 16
16
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 0.5 ppm
1.
43
11
.4
62
1.
47
41
.6
22
1.
63
31
.6
54
1.
66
01
.6
92
1.
70
31
.7
43
1.
86
41
.8
77
1.
89
21
.8
97
1.
90
32
.0
61
2.
07
92
.0
90
2.
11
02
.1
17
2.
12
62
.1
36
2.
32
82
.3
48
2.
37
02
.4
23
2.
45
12
.4
73
2.
49
32
.5
15
3.
67
83
.6
89
4.
40
14
.4
12
4.
42
64
.4
37
4.
45
14
.4
62
6.
14
86
.1
72
6.
20
16
.2
25
6.
57
76
.6
30
7.
22
97
.2
38
7.
25
37
.2
57
7.
28
17
.3
06
7.
32
97
.3
69
7.
39
4
1.
05
2.
22
1.
07
2.
06
3.
07
0.
99
1.
00
0.
99
0.
99
5.
13
200 180 160 140 120 100 80 60 40 20 ppm
24.86
27.38
27.62
42.61
55.60
70.62
76.61
77.04
77.46
126.42
127.56
128.55
129.01
130.86
136.78
214.33
O OH
2oPh
O OH
2oPh
Page 17
17
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 0.5 ppm
-0
.0
22
1.
59
22
.4
33
2.
48
02
.6
45
2.
66
92
.6
84
2.
70
72
.7
31
2.
75
52
.8
83
2.
89
22
.9
05
2.
91
52
.9
25
2.
93
82
.9
48
2.
96
62
.9
79
3.
65
63
.6
66
3.
69
43
.7
04
3.
73
33
.7
46
3.
78
23
.8
16
3.
83
83
.8
53
3.
87
64
.1
94
4.
21
84
.2
24
4.
23
14
.2
55
4.
95
24
.9
62
4.
97
84
.9
90
5.
52
4
7.
24
47
.4
79
7.
50
8
8.
18
88
.2
16
1.
06
1.
09
2.
06
3.
23
1.
06
1.
00
2.
09
2.
04
200 180 160 140 120 100 80 60 40 20 ppm
43.07
57.20
67.53
68.30
68.87
76.55
76.97
77.39
123.68
126.33
148.03
208.24
O
O OH
NO2
2p
O
O OH
NO2
2p
Page 18
18
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 0.5 ppm
-0
.0
19
2.
48
82
.4
97
2.
51
92
.5
27
2.
76
92
.7
85
2.
80
12
.8
17
2.
87
32
.8
87
2.
89
62
.9
02
2.
91
82
.9
30
2.
93
92
.9
54
2.
97
42
.9
85
2.
99
93
.0
18
3.
03
23
.0
50
3.
07
13
.0
89
3.
10
1
5.
50
5
7.
24
77
.4
91
7.
52
0
8.
19
68
.2
25
0.
99
2.
12
4.
08
1.
11
1.
00
2.
06
2.
00
200 180 160 140 120 100 80 60 40 20 ppm
29
.4
63
0.
80
45
.0
4
59
.2
3
70
.2
47
6.
60
77
.0
27
7.
44
12
3.
69
12
6.
69
14
7.
32
14
8.
14
21
0.
93
S
O OH
NO2
2q
S
O OH
NO2
2q
Page 19
19
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 0.5 ppm
0.
00
01
.6
51
1.
69
21
.7
02
1.
71
21
.9
71
1.
98
81
.9
93
2.
00
52
.0
15
2.
03
22
.0
78
2.
12
22
.4
17
2.
41
92
.4
53
2.
46
42
.4
69
2.
48
02
.7
08
2.
73
22
.9
41
2.
94
62
.9
49
2.
96
22
.9
74
3.
83
83
.8
45
3.
85
23
.8
67
3.
86
93
.8
81
3.
88
93
.8
96
3.
91
33
.9
18
3.
92
33
.9
29
3.
93
63
.9
40
3.
94
65
.4
17
5.
42
75
.4
36
7.
24
37
.2
62
7.
26
77
.2
72
7.
29
67
.3
15
7.
32
27
.3
35
7.
33
8
1.
36
3.
16
1.
06
1.
07
2.
04
4.
24
1.
00
5.
33
200 180 160 140 120 100 80 60 40 20 ppm
32.91
34.37
38.59
53.19
64.46
64.71
70.13
76.61
77.03
77.45
107.59
125.64
127.04
128.25
141.06
212.67
O OH
2r
O O
O OH
2r
O O
Page 20
20
HPLC traces
O OH
OMe2a
O OH
OMe2a
Page 21
21
O OH
NO2
2b
O OH
NO2
2b
Page 22
22
O OH
2c
O OH
2c
Page 23
23
O OH
2dCH3
O OH
2dCH3
Page 24
24
O OH
2e
O OH
2e
Page 25
25
O OH
2fNO2
O OH
2fNO2
Page 26
26
O OH
2g
F
O OH
2g
F
Page 27
27
O OH
2hCl
O OH
2hCl
Page 28
28
O OH
2iCl
Cl
O OH
2iCl
Cl
Page 29
29
O OH
2j
O OH
2j
Page 30
30
O OH
2k
OMe
OMe
O OH
2k
OMe
OMe
Page 31
31
O OH
2lO
O
O OH
2lO
O
Page 32
32
O OH
Ph2m
O OH
Ph2m
Page 33
33
O OH2n N
O
O OH2n N
O
Page 34
34
O OH
2oPh
O OH
2oPh
Page 35
35
O
O OH
NO2
2p
O
O OH
NO2
2p
Page 36
36
S
O OH
NO2
2q
S
O OH
NO2
2q
Page 37
37
O OH
2r
O O
O OH
2r
O O
Page 38
38
Representative 1H NMR of crude reaction mixture for the transfer aldol of rac-2b
rac-2b
[BMIM]BF4, 50 oC
O OH O OH
(S, S)-2b
NO2NO2
1 (20 mol%)
acetone
O OH
NO2
+
10 9 8 7 6 5 4 3 2 1 0 ppm
4.
77
74
.8
15
4.
84
45
.1
77
5.
19
25
.2
02
5.
21
75
.4
13
7.
15
97
.1
94
7.
40
67
.4
34
7.
45
97
.4
87
8.
12
38
.1
29
8.
15
2
0.
03
1.
30
1.
00
0.
01
O OH
(S, S)-2b
NO2
O OH
NO2