S1 Supporting Information Total Synthesis of Mangiferin, Homomangiferin, and Neomangiferin Xiong Wei, † Danlin Liang, † Qing Wang, † Xiangbao Meng,* ,† and Zhongjun Li* ,†,‡ † The State Key Laboratory of Natural and Biomimetic Drugs Department of Chemical Biology, School of Pharmaceutical Sciences Peking University, Beijing 100191, P R China ‡ National Research Center for Carbohydrate Synthesis Jiangxi Normal University, Nanchang 330022, China Email: [email protected] or [email protected] Contents Page General Information S2 Experimental Section S3~S4 NMR Spectrum of Compounds S5~S79 Data for natural and synthetic Mangiferin xanthonoids S80~S85 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is © The Royal Society of Chemistry 2016
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-
S1
Supporting Information
Total Synthesis of Mangiferin, Homomangiferin, and Neomangiferin
Xiong Wei,† Danlin Liang,† Qing Wang,† Xiangbao Meng,*,† and Zhongjun Li*,†,‡
†The State Key Laboratory of Natural and Biomimetic Drugs
Department of Chemical Biology, School of Pharmaceutical Sciences
Peking University, Beijing 100191, P R China ‡National Research Center for Carbohydrate Synthesis
Jiangxi Normal University, Nanchang 330022, China
Email: [email protected] or [email protected]
Contents Page
General Information S2
Experimental Section S3~S4
NMR Spectrum of Compounds S5~S79
Data for natural and synthetic Mangiferin xanthonoids S80~S85
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016
-
S2
1. General Information:
Melting points were uncorrected. Nuclear magnetic resonance spectra (NMR spectra) were recorded using 400 MHz equipments
(400 MHz for 1H; 100 MHz for 13C). All spectra obtained in CDCl3 were referenced to tetramethylsilane at 0.00 ppm for 1H spectra and
77.16 ppm for 13C spectra. Spectra obtained in DMSO-d6 were referenced to DMSO at 2.50 ppm for 1H spectra and 39.52 ppm for 13C
spectra. The following abbreviations are used for the multiplicities: s: singlet, d: doublet, t: triplet, q: quartet, m: multiplet, br s: broad
singlet, br d: broad doublet. High resolution mass spectra (HRMS) data were performed with an ionization mode of ESI (electron spray
ionization). Optical rotations were measured using sodium D line. Analytical thin layer chromatography (TLC) was performed on Silica
gel 60 F254 precoated on aluminiumplates, with detection by fluorescence and (or) by staining with 5% concentrated sulfuric acid in
ethanol. Flash column chromatography was performed using Silica gel (230~400 mesh) with solvents distilled prior to use.
Unless otherwise noted, all the reagents were obtained from commercial suppliers and used without further purification. The
following abbreviations are used: PE: petroleum ether (b.p. 60~90°); EtOAc: ethyl acetate; DCM: dichloromethane; THF:
tetrahydrofuran; DMSO: dimethyl sulfoxide; DMF: N,N-dimethylformamide; NBS: N-bromosuccinimide; DIPEA: N,N-diisopropyl
ethyl amine; TMSOTf: trimethylsilyl trifluoromethanesulfonate; TBAB: tetrabutyl ammonium bromide.
-
S3
2. Experimental Section 2,3,4,6-Tetra-O-benzyl-α/β-D-glucopyranoside (5).
Building block 5 was obtained from commercial suppliers or prepared following the above synthetic route.
1) Glucose pentaacetate (10.0 g, 25.6 mmol) and p-thiocresol (4.8 g, 38.4 mmol) were dissolved in anhydrous DCM (200 mL) under
atmosphere of nitrogen, and BF3·Et2O (4.2 mL, 33.3 mmol) was added. After being stirred overnight at room temperature, the reaction
mixture was diluted with DCM and washed with saturated NaHCO3 (aq), 1N HCl (aq) and brine. The combined organic layers were dried
over Na2SO4, concentrated, and purified by flash column chromatography (PE-EtOAc, 1:1), affording S1 (10.4 g, 90%) as a white solid.
2) To a solution of thioglycoside S1 (10.4 g, 22.8 mmol) in methanol (100 ml) was added appropriate amount of sodium at room
temperature, adjusting pH to 11~12. After being stirred for 1 h, the reaction mixture was neutralized with DOWEX 50WX8-400 resin (H+
form), filtered, and evaporated in vacuo, affording S2 (6.6 g, quant) as a white solid without purification.
3) The obtained S2 was dissolved in DMF (200 mL) and cooled to 0 °C, and NaH (60%, 5.8 g) was added gradually in portions.
When no gas generating, BnBr (16 mL, 136.6 mmol) was added dropwise with a funnel, and the suspension was then allowed to warm to
room temperature. After being stirred overnight, appropriate amount of methanol was added to quench the reaction, and the solvent was
-
S4
removed under reduced pressure. The residue was washed with brine and extracted with EtOAc. The combined organic layers were dried
over Na2SO4, concentrated, and purified by flash column chromatography (PE-EtOAc, 15:1) to afford S3 (13.2 g, 89%) as a yellow syrup: 1H NMR (400 MHz, CDCl3) δ 7.55 – 6.95 (m, 24H), 5.02 – 4.67 (m, 5H), 4.67 – 4.48 (m, 4H), 3.85 – 3.57 (m, 4H), 3.49 (m, 2H), 2.29 (s,
3H) ppm; 13C NMR (100 MHz, CDCl3) δ 138.5, 138.4, 138.2, 138.1, 137.8, 132.8, 129.9, 129.8, 128.5, 128.4, 128.3, 128.0, 127.9, 127.9,
127.8, 127.7, 127.6, 87.7, 86.9, 80.9, 79.2, 77.9, 75.9, 75.5, 75.1, 73.5, 69.1, 21.2 ppm.
4) To a solution of benzylated thioglycoside S3 (1.0 g, 1.55 mmol) in acetone/H2O (16 mL, 9:1 v/v) was added NBS (0.83 g, 4.66
mmol) under exclusion of light. After being stirred for 3 h at rt, the reaction mixture was neutralized with appropriate amount of Et3N
and evaporated under reduced pressure. The residue was washed with brine and extracted with DCM, and the combined organic layers
were dried over Na2SO4, concentrated, and purified by flash column chromatography (PE-acetone, 5:1) to afford 5 (738 mg, 88%) as a
white solid: 1H NMR (400 MHz, CDCl3) δ 7.39 – 7.08 (m, 20H), 5.22 (t, J = 3.0 Hz, 0.8H), 4.98 – 4.43 (m, 8.2H), 4.07 – 3.49 (m, 6H),
3.44 – 3.34 (m, 0.2H), 3.10 (d, J = 2.4 Hz, 0.8H) ppm; 13C NMR (100 MHz, CDCl3) δ 138.8/138.7, 138.5/138.4, 138.1/138.0, 137.9,
130.1, 128.6, 128.5, 128.4, 128.3, 128.2, 128.1, 128.0, 128.0, 127.9, 127.8, 127.7, 97.6/91.4, 84.7/83.3, 81.9/80.1, 78.0/77.9, 75.8,
75.1/74.8, 73.6, 73.3, 70.4, 69.1/68.8 ppm.
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S5
1H NMR spectrum of Synthetic Mangiferin 1 (DMSO-d6, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
12.
496
2.50
02.
505
2.50
93.
095
3.11
73.
139
3.14
73.
166
3.17
53.
197
3.21
73.
349
3.38
13.
395
3.41
03.
423
3.67
13.
699
4.02
24.
043
4.06
54.
479
4.57
64.
600
4.85
56.
366
6.85
97.
375
10.5
32
13.7
53
3.14
32.
196
1.05
71.
000
1.04
22.
052
2.00
0
1.03
1
1.04
1
1.04
2
2.98
2
1.05
3
OHO
OHOH
HOHO
HO OH
OH
Mangiferin (1)
O
O
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S6
13C NMR spectrum of Synthetic Mangiferin 1 (DMSO-d6, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
5
61.8
0
70.7
470
.93
73.4
879
.25
81.7
3
93.8
110
1.69
103.
0010
7.67
108.
4411
2.10
143.
91
151.
1215
4.19
156.
6116
2.08
164.
05
179.
42
OHO
OHOH
HOHO
HO OH
OH
Mangiferin (1)
O
O
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S7
1H NMR spectrum of Synthetic Homomangiferin 2 (DMSO-d6, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
62.
500
2.50
43.
032
3.05
53.
079
3.10
43.
130
3.14
83.
165
3.18
83.
210
3.35
33.
674
3.70
23.
854
3.88
53.
959
3.98
24.
005
4.17
54.
199
4.21
94.
441
4.55
14.
576
4.60
44.
628
4.86
46.
633
6.64
06.
891
7.39
07.
399
13.6
78
4.09
71.
140
2.92
90.
512
0.55
60.
986
1.89
51.
947
1.02
01.
000
1.00
0
2.06
8
1.01
6
OMeO
OHOH
HOHO
HO OH
OHO
O
Homomangiferin (2)
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S8
1H NMR spectrum of Synthetic Homomangiferin 2 (DMSO-d6+D2O, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
62.
500
2.50
43.
043
3.06
73.
090
3.11
33.
135
3.14
63.
153
3.17
43.
191
3.21
33.
327
3.34
23.
356
3.36
93.
384
3.68
13.
836
3.86
53.
950
3.97
43.
997
4.14
74.
171
4.19
34.
551
4.57
64.
593
4.61
76.
613
6.62
26.
902
7.39
07.
397
3.12
01.
042
1.19
13.
085
0.52
30.
493
1.04
8
1.00
51.
014
1.00
0
OMeO
OHOH
HOHO
HO OH
OHO
O
Homomangiferin (2)
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S9
13C NMR spectrum of Synthetic Homomangiferin 2 (DMSO-d6+D2O, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
556
.54
56.7
961
.87
69.8
870
.47
70.9
271
.00
72.9
273
.13
78.8
079
.13
79.4
681
.82
81.9
790
.21
91.0
310
2.15
102.
6410
2.86
108.
2510
8.55
112.
22
144.
0815
1.24
151.
3115
4.36
157.
1215
7.22
160.
5916
1.30
164.
5416
5.71
179.
3917
9.71
OMeO
OHOH
HOHO
HO OH
OHO
O
Homomangiferin (2)
-
S10
1H-1H COSY spectrum of Synthetic Homomangiferin 2 (DMSO-d6+D2O)
-
S11
HSQC spectrum of Synthetic Homomangiferin 2 (DMSO-d6+D2O)
-
S12
HMBC spectrum of Synthetic Homomangiferin 2 (DMSO-d6+D2O)
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S13
1H NMR spectrum of Synthetic Neomangiferin 3 (DMSO-d6+D2O, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.12
83.
150
3.17
53.
187
3.20
03.
209
3.22
23.
230
3.24
43.
304
3.32
13.
325
3.33
33.
340
3.38
23.
396
3.40
83.
425
3.45
03.
508
3.52
13.
538
3.55
23.
606
3.65
73.
684
3.71
04.
018
4.04
14.
063
4.57
94.
603
4.89
84.
916
6.40
66.
955
7.70
2
5.21
65.
337
1.08
1
1.03
31.
054
1.02
2
1.00
0
1.09
0
Neomanferin (3)
OOHO
OH O
OH
OOH
HOHO
HO
O
HO
OHOH
OH
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S14
13C NMR spectrum of Synthetic Neomangiferin 3 (DMSO-d6+D2O, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
560
.69
61.6
069
.67
70.3
770
.70
73.2
773
.37
75.9
277
.29
78.9
981
.70
93.7
910
1.53
102.
1010
3.45
107.
9311
0.47
112.
03
143.
74
152.
7615
4.96
156.
5416
1.73
164.
21
179.
24
Neomanferin (3)
OOHO
OH O
OH
OOH
HOHO
HO
O
HO
OHOH
OH
-
S15
1H-1H COSY spectrum of Synthetic Neomangiferin 3 (DMSO-d6+D2O)
-
S16
HSQC spectrum of Synthetic Neomangiferin 3 (DMSO-d6+D2O)
-
S17
HMBC spectrum of Synthetic Neomangiferin 3 (DMSO-d6+D2O)
-
S18
1H NMR spectrum of Compound S3 (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.28
82.
293
3.48
13.
490
3.63
33.
644
3.65
53.
671
3.68
63.
698
3.70
83.
730
3.73
73.
770
3.79
54.
511
4.52
04.
549
4.59
24.
605
4.61
24.
712
4.72
24.
737
4.80
54.
814
4.83
04.
853
4.86
44.
885
4.90
87.
017
7.02
77.
186
7.19
77.
272
7.29
07.
300
7.33
87.
394
7.40
07.
482
7.49
27.
497
3.00
0
2.01
04.
045
4.14
01.
090
3.97
4
24.9
16
STolO
OBn
BnOBnO
BnO
S3
-
S19
13C NMR spectrum of Compound S3 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
21.2
1
69.1
473
.50
75.1
375
.46
75.9
176
.84
77.1
677
.48
77.9
279
.17
80.8
986
.86
87.7
412
7.62
127.
7512
7.79
127.
9012
7.93
128.
0312
8.31
128.
4312
8.52
129.
7512
9.85
132.
7913
7.75
138.
1613
8.21
138.
4513
8.51
STolO
OBn
BnOBnO
BnO
S3
-
S20
1H NMR spectrum of Compound 5 (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
03.
098
3.10
43.
555
3.55
93.
569
3.58
33.
591
3.61
43.
640
3.64
53.
676
3.68
63.
712
3.94
73.
970
3.99
44.
023
4.46
04.
473
4.49
04.
500
4.54
04.
559
4.57
24.
603
4.67
04.
699
4.74
74.
777
4.80
74.
815
4.82
14.
833
4.84
84.
931
4.95
85.
212
5.22
05.
227
7.12
37.
128
7.13
97.
146
7.24
37.
258
7.26
37.
270
7.27
67.
298
7.31
27.
319
7.32
97.
334
7.34
9
0.80
40.
233
4.57
8
1.62
4
8.58
1
0.80
0
20.9
39
OHO
OBnBnO
BnO
BnO
5
-
S21
13C NMR spectrum of Compound 5 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
68.7
669
.06
70.4
073
.32
73.5
974
.82
75.1
075
.76
75.8
076
.84
77.1
677
.36
77.4
877
.87
77.9
780
.14
81.8
783
.26
84.7
191
.38
97.6
212
7.71
127.
7812
7.80
127.
8312
7.88
127.
9612
8.03
128.
0612
8.15
128.
2412
8.36
128.
4812
8.60
130.
1313
7.93
138.
0013
8.12
138.
3513
8.51
138.
6713
8.83
OHO
OBn
BnOBnO
BnO
5
-
S22
1H NMR spectrum of Compound 5e (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.97
02.
059
3.63
83.
642
3.66
03.
668
3.68
43.
692
3.71
53.
724
3.74
93.
772
3.93
73.
960
4.42
24.
452
4.49
44.
520
4.55
04.
580
4.60
64.
658
4.68
64.
804
4.83
14.
857
4.94
54.
972
6.38
76.
396
7.12
27.
126
7.12
97.
140
7.14
57.
199
7.20
57.
213
7.22
37.
228
7.23
37.
238
7.24
37.
255
7.26
37.
280
7.28
27.
290
7.30
37.
307
7.31
07.
322
7.32
57.
341
7.34
6
3.00
0
4.48
61.
601
8.13
7
0.21
1
0.78
6
20.0
96
O
OBn
BnOBnO
BnO
5e
OAc
-
S23
13C NMR spectrum of Compound 5e (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.8
320
.88
67.9
972
.73
72.9
873
.29
73.3
374
.77
74.8
075
.08
75.3
275
.47
76.8
276
.84
77.0
777
.16
77.4
878
.75
80.9
181
.52
84.6
289
.81
93.8
812
7.48
127.
5312
7.59
127.
6412
7.67
127.
7912
7.96
128.
0612
8.21
128.
2512
8.32
137.
5013
7.70
137.
7613
7.94
138.
0213
8.28
138.
5316
9.00
169.
13
O
OBn
BnOBnO
BnO
5e
OAc
-
S24
1H NMR spectrum of Compound 8a (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.68
03.
748
3.76
73.
774
3.79
73.
852
3.87
63.
885
3.89
44.
111
4.13
84.
386
4.49
94.
512
4.52
94.
538
4.71
94.
746
4.75
64.
786
4.90
84.
913
4.93
34.
956
6.08
86.
094
6.14
86.
153
6.91
76.
927
6.93
06.
935
6.94
17.
146
7.15
47.
162
7.21
97.
237
7.24
77.
261
7.27
17.
278
7.28
27.
294
7.29
97.
308
7.31
27.
323
7.32
97.
333
7.34
07.
344
7.35
67.
373
7.37
7
1.06
53.
104
8.12
02.
065
1.01
31.
016
2.05
02.
037
4.00
1
2.08
6
2.00
018
.329
OMeO
OMeOBn
BnOBnO
BnO OMe
8a
-
S25
13C NMR spectrum of Compound 8a (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.2
555
.77
56.0
669
.12
72.6
973
.16
74.4
575
.08
75.8
376
.84
77.1
677
.48
78.4
679
.66
80.0
287
.55
90.8
491
.77
107.
7512
7.21
127.
3812
7.61
127.
9812
8.03
128.
0812
8.17
128.
2012
8.37
128.
4213
8.45
138.
6413
8.95
139.
0015
9.85
160.
9416
1.39
OMeO
OMeOBnBnO
BnO
BnO OMe
8a
-
S26
1H NMR spectrum of Compound 8b (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.71
03.
776
4.15
84.
185
4.46
64.
473
4.49
34.
503
4.57
74.
622
4.82
14.
847
4.88
94.
924
4.97
04.
977
4.99
35.
037
5.05
45.
061
6.25
26.
920
6.92
46.
939
6.94
37.
109
7.12
77.
132
7.13
57.
180
7.19
37.
199
7.21
07.
213
7.21
97.
229
7.23
57.
245
7.25
17.
262
7.26
67.
276
7.28
57.
298
7.30
17.
306
7.31
17.
325
7.32
77.
343
7.35
97.
360
7.47
37.
478
7.48
7
1.05
94.
084
1.00
81.
068
2.02
82.
044
10.3
14
2.00
0
2.03
531
.695
2.05
1
OBnO
OBnOBn
BnOBnO
BnO OBn
8b
-
S27
13C NMR spectrum of Compound 8b (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
69.5
170
.17
70.8
171
.38
73.4
173
.50
74.1
175
.06
75.3
876
.84
77.1
677
.48
78.4
479
.47
79.8
387
.75
94.3
094
.86
109.
4412
7.17
127.
2312
7.28
127.
4612
7.50
127.
5612
7.64
127.
6912
7.76
127.
8812
7.97
128.
0512
8.06
128.
0912
8.13
128.
3512
8.36
128.
4312
8.44
128.
5512
8.70
136.
8313
7.28
138.
5213
8.62
138.
8913
9.19
159.
2816
0.07
160.
35
OBnO
OBnOBn
BnOBnO
BnO OBn
8b
-
S28
1H NMR spectrum of Compound 9b (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.72
73.
738
3.75
03.
763
3.78
63.
812
3.83
63.
853
3.87
33.
886
3.90
54.
179
4.46
44.
472
4.49
44.
574
4.60
14.
613
4.64
14.
677
4.86
04.
884
4.90
34.
938
6.12
76.
206
6.87
96.
887
6.89
96.
903
6.91
26.
921
7.11
27.
117
7.12
57.
129
7.14
17.
145
7.20
67.
222
7.22
67.
234
7.24
47.
260
7.26
57.
274
7.28
77.
303
7.31
97.
324
7.32
77.
335
7.35
610
.249
10.3
24
1.08
413
.602
1.03
41.
150
8.39
7
1.00
0
2.01
518
.715
0.93
4O
MeO
OMeOBnBnO
BnO
BnO OMe
9b
CHO
-
S29
13C NMR spectrum of Compound 9b (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.6
456
.01
56.0
656
.09
64.3
965
.51
69.4
772
.26
73.1
973
.28
74.4
574
.75
75.0
775
.13
75.5
175
.92
76.8
477
.16
77.4
878
.81
78.9
979
.86
80.7
087
.43
87.9
090
.77
91.9
211
4.11
127.
3512
7.36
127.
4512
7.50
127.
5812
7.61
127.
6912
7.87
127.
9212
8.00
128.
0512
8.15
128.
2512
8.32
128.
3912
8.43
128.
5013
8.17
138.
2213
8.41
138.
4713
8.50
138.
8013
8.99
163.
9416
4.28
165.
1716
5.30
187.
7418
7.78
OMeO
OMeOBnBnO
BnO
BnO OMe
9b
CHO
-
S30
1H NMR spectrum of Compound 9c (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.64
83.
670
4.22
24.
468
4.55
64.
581
4.60
64.
798
4.81
24.
825
4.83
64.
844
4.85
14.
869
4.87
84.
984
5.04
95.
077
5.13
85.
151
5.15
76.
266
6.88
17.
077
7.08
57.
101
7.14
07.
168
7.18
87.
208
7.21
37.
220
7.22
67.
234
7.24
27.
257
7.26
87.
291
7.30
17.
315
7.33
47.
337
7.35
27.
356
7.36
27.
374
7.37
77.
381
7.39
97.
438
7.45
77.
480
7.49
810
.354
10.4
72
5.25
1
6.22
3
10.9
37
1.00
0
2.01
4
34.8
65
0.95
9O
BnO
OBnOBn
BnOBnO
BnO OBn
9c
CHO
-
S31
13C NMR spectrum of Compound 9c (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
69.1
570
.42
70.8
673
.46
73.7
474
.23
75.0
975
.39
76.8
477
.16
77.4
878
.22
78.4
578
.70
79.4
087
.91
94.9
011
4.12
126.
9412
6.97
127.
0812
7.18
127.
3712
7.56
127.
6412
7.68
127.
7112
7.77
127.
8412
8.01
128.
0312
8.07
128.
0912
8.15
128.
1912
8.29
128.
3212
8.33
128.
3812
8.40
128.
4512
8.56
128.
5812
8.74
128.
7612
8.82
135.
8313
5.96
135.
9813
6.77
138.
2313
8.28
138.
2913
8.80
162.
1016
2.91
164.
0918
7.56
OBnO
OBnOBn
BnOBnO
BnO OBn
9c
CHO
-
S32
1H NMR spectrum of Compound 10a (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.50
93.
514
3.52
9
5.15
05.
168
5.19
9
7.04
37.
342
9.20
9
4.03
62.
098
1.01
81.
000
OMOM
OMOM
MOMO
Br10a
-
S33
13C NMR spectrum of Compound 10a (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
56.0
256
.11
56.2
1
76.8
477
.16
77.4
8
95.5
695
.80
96.0
210
4.54
106.
71
121.
54
142.
7314
7.25
149.
03
OMOM
OMOM
MOMO
Br10a
-
S34
1H NMR spectrum of Compound 11a (DMSO-d6, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
62.
500
2.50
43.
543
3.58
03.
596
3.61
13.
620
3.63
63.
657
3.67
73.
705
3.72
63.
773
3.85
23.
867
4.17
44.
197
4.42
84.
452
4.45
94.
491
4.49
94.
527
4.54
34.
568
4.59
04.
621
4.73
84.
766
4.77
84.
805
4.81
94.
833
4.85
24.
880
6.35
96.
607
6.63
16.
657
6.94
86.
964
7.20
17.
206
7.21
07.
218
7.25
17.
269
7.28
27.
295
7.30
17.
326
7.33
112
.195
12.2
13
11.3
843.
036
1.01
95.
517
3.52
3
1.02
22.
000
2.05
518
.645
0.94
9
0.94
3
0.99
0O
MeO
OMeOBn
BnOBnO
BnO OH
OH
OMe OH
11aO
-
S35
13C NMR spectrum of Compound 11a (DMSO-d6, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
556
.04
56.0
756
.35
63.4
669
.07
71.7
672
.26
72.9
073
.48
73.5
974
.06
74.1
374
.49
74.7
178
.04
78.2
578
.75
86.0
886
.75
93.2
810
2.77
112.
1611
2.80
113.
1011
4.93
127.
2712
7.37
127.
4212
7.46
127.
5712
7.70
127.
8312
7.91
128.
0112
8.12
128.
1812
8.22
137.
9913
8.21
138.
3313
8.36
138.
4613
8.81
138.
8615
5.36
157.
2815
7.41
158.
1216
0.02
161.
3919
7.34
OMeO
OMeOBn
BnOBnO
BnO OH
OH
OMe OH
11aO
-
S36
1H NMR spectrum of Compound 11b (DMSO-d6, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
52.
500
2.50
43.
506
3.53
04.
387
4.41
54.
424
4.43
14.
465
4.47
74.
533
4.56
14.
618
4.64
34.
685
4.71
34.
727
4.75
64.
770
4.81
54.
841
5.11
75.
167
5.19
95.
215
5.22
96.
373
6.38
26.
876
7.09
97.
104
7.11
37.
122
7.14
87.
158
7.16
57.
173
7.19
17.
216
7.23
07.
236
7.24
77.
257
7.26
67.
271
7.27
87.
282
7.29
57.
302
7.31
07.
317
7.56
17.
570
7.58
4
5.23
5
1.26
8
15.8
04
0.94
0
38.9
29
0.97
2
0.84
9
1.00
0O
BnO
OBnOBnBnO
BnO
BnO OH
OH
OBn OH
11bO
-
S37
13C NMR spectrum of Compound 11b (DMSO-d6, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
569
.19
70.1
170
.22
71.0
072
.65
72.7
173
.56
73.7
274
.28
74.4
574
.55
77.9
578
.16
78.9
086
.83
96.0
510
2.94
113.
1011
3.16
127.
2612
7.34
127.
4412
7.63
127.
7212
7.85
127.
9812
8.01
128.
0712
8.21
128.
3212
8.39
128.
4412
8.47
128.
5612
8.61
128.
6512
8.77
136.
5713
6.70
136.
9113
7.93
138.
0313
8.20
138.
3113
8.72
138.
8615
5.63
156.
5315
8.39
160.
3219
7.40
OBnO
OBnOBnBnO
BnO
BnO OH
OH
OBn OH
11bO
-
S38
1H NMR spectrum of Compound 12 (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.43
53.
486
3.48
9
5.07
85.
079
5.12
15.
123
5.18
55.
186
6.62
26.
628
6.63
56.
643
6.65
16.
657
6.87
86.
884
6.89
17.
024
7.03
27.
039
7.04
57.
054
3.02
55.
996
2.03
12.
001
2.03
4
1.00
51.
000
1.01
2
OMOM
OMOM
MOMO
12
-
S39
13C NMR spectrum of Compound 12 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.5
555
.75
55.8
6
76.8
477
.16
77.4
8
94.7
595
.21
96.0
0
106.
2410
9.04
118.
06
142.
03
148.
0515
2.76
OMOM
OMOM
MOMO
12
-
S40
1H NMR spectrum of Compound 14a (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.19
33.
224
3.37
93.
467
3.49
23.
656
3.70
63.
719
3.73
63.
752
3.77
93.
857
4.46
34.
475
4.48
24.
506
4.66
94.
704
4.77
14.
840
4.84
34.
884
4.88
74.
896
4.91
14.
982
4.98
85.
115
5.12
25.
228
5.24
05.
247
6.26
56.
314
6.87
06.
906
7.01
47.
024
7.02
97.
034
7.18
07.
186
7.19
57.
215
7.23
57.
247
7.26
07.
268
7.27
87.
285
7.29
77.
308
7.31
17.
471
7.60
9
3.01
53.
134
4.05
213
.069
0.45
40.
570
12.2
38
3.08
5
1.00
00.
459
0.54
92.
080
18.2
940.
464
0.55
2
OMeO
OMeOBn
BnOBnO
BnO OMOM
OMOM
OMe OMOM
14aO
-
S41
13C NMR spectrum of Compound 14a (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.9
856
.03
56.0
956
.13
56.2
556
.32
56.5
563
.84
64.1
872
.57
73.2
073
.32
73.7
974
.32
75.1
175
.57
75.9
276
.84
77.1
677
.48
78.3
378
.55
78.8
079
.43
79.8
180
.88
87.1
987
.86
92.8
195
.18
95.5
196
.01
96.1
896
.31
104.
6912
0.06
127.
3912
7.50
127.
5512
7.68
127.
7012
7.80
127.
9412
8.02
128.
0412
8.08
128.
1512
8.21
128.
3012
8.38
128.
4512
8.48
138.
4113
8.59
138.
8315
3.79
158.
1616
1.17
OMeO
OMeOBnBnO
BnO
BnO OMOM
OMOM
OMe OMOM
14aO
-
S42
1H NMR spectrum of Compound 14b (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.00
43.
013
3.22
33.
326
3.38
83.
394
3.56
84.
399
4.46
14.
492
4.57
64.
650
4.66
64.
676
4.72
34.
744
4.75
24.
784
4.86
44.
876
4.89
64.
954
4.95
84.
975
4.99
15.
122
5.13
85.
143
6.25
36.
808
6.92
87.
019
7.03
37.
038
7.06
37.
072
7.07
47.
081
7.09
07.
100
7.11
37.
121
7.12
97.
132
7.14
07.
144
7.15
87.
163
7.16
87.
179
7.18
67.
190
7.20
47.
390
7.51
1
2.84
4
11.1
93
0.31
70.
705
19.0
18
2.14
8
0.90
3
0.32
80.
716
35.9
61
0.71
4
OBnO
OBnOBn
BnOBnO
BnO OMOM
OMOM
OBn OMOM
14bO
-
S43
13C NMR spectrum of Compound 14b (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
56.0
456
.27
56.4
970
.54
70.8
373
.37
74.1
074
.16
75.1
175
.42
76.8
477
.16
77.4
878
.23
78.3
879
.06
79.3
887
.78
95.1
395
.41
96.2
312
3.70
126.
8912
6.94
127.
1312
7.34
127.
4012
7.48
127.
5112
7.64
127.
7512
7.80
127.
8612
7.89
127.
9512
8.03
128.
1012
8.15
128.
2312
8.26
128.
2912
8.32
128.
3612
8.38
128.
4512
8.49
128.
6513
6.57
136.
8313
7.35
138.
3613
8.41
138.
9014
1.58
152.
2015
3.78
157.
3116
0.07
OBnO
OBnOBn
BnOBnO
BnO OMOM
OMOM
OBn OMOM
14bO
-
S44
1H NMR spectrum of Compound 15a (DMSO-d6, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.50
02.
504
3.07
33.
193
3.39
13.
414
3.57
63.
601
3.61
93.
643
3.66
73.
676
3.77
03.
775
3.84
23.
887
4.40
24.
451
4.48
64.
558
4.57
24.
581
4.59
64.
611
4.62
34.
774
4.78
84.
802
4.81
64.
822
4.83
34.
864
5.31
35.
334
6.60
76.
671
6.70
96.
719
6.93
36.
956
6.96
56.
974
7.19
07.
199
7.20
47.
220
7.24
57.
251
7.26
87.
285
7.29
37.
307
7.31
512
.220
12.2
29
2.74
43.
045
11.1
763.
053
0.51
20.
529
11.3
31
2.05
1
0.93
41.
012
2.95
318
.830
1.00
0
OMeO
OMeOBn
BnOBnO
BnO OMOM
OMOM
OMe OH
15aO
-
S45
13C NMR spectrum of Compound 15a (DMSO-d6, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
555
.54
55.9
756
.02
56.0
856
.20
56.2
256
.34
63.5
572
.19
72.2
973
.28
74.0
474
.09
74.4
274
.67
77.9
778
.80
86.7
394
.34
94.3
895
.87
96.0
210
3.28
112.
2611
4.04
114.
1612
7.30
127.
4012
7.46
127.
5112
7.55
127.
6112
7.67
127.
8012
8.02
128.
1913
8.12
138.
1913
8.32
138.
3613
8.47
138.
5713
8.77
138.
8815
5.45
157.
4315
7.52
159.
5215
9.58
160.
3816
1.79
OMeO
OMeOBn
BnOBnO
BnO OMOM
OMOM
OMe OH
15aO
-
S46
1H NMR spectrum of Compound 15b (DMSO-d6, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
12.
495
2.50
02.
505
2.50
93.
132
3.39
43.
417
3.61
54.
380
4.44
44.
487
4.50
44.
651
4.67
64.
698
4.72
64.
756
4.76
54.
781
5.20
45.
325
5.34
96.
720
6.74
26.
909
6.92
87.
040
7.12
27.
131
7.13
47.
145
7.16
37.
170
7.17
87.
182
7.19
07.
201
7.22
57.
234
7.23
87.
245
7.25
27.
256
7.26
37.
268
7.27
17.
282
7.28
57.
290
7.29
47.
306
7.31
47.
321
12.1
24
0.93
12.
098
1.06
42.
069
5.12
80.
368
0.69
112
.215
0.72
60.
352
6.48
3
1.05
43.
109
32.9
872.
116
1.00
0O
BnO
OBnOBn
BnOBnO
BnO OMOM
OMOM
OBn OH
15bO
-
S47
13C NMR spectrum of Compound 15b (DMSO-d6, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.8
939
.10
39.3
139
.52
39.7
339
.94
40.1
555
.52
55.5
456
.16
69.9
770
.02
72.4
372
.47
73.3
774
.06
74.2
378
.05
78.7
594
.30
95.7
495
.81
103.
3311
3.18
114.
3312
6.98
127.
2312
7.41
127.
4712
7.50
127.
6012
7.74
127.
7812
7.83
127.
8712
7.98
128.
0212
8.14
128.
1812
8.22
128.
3012
8.40
128.
5213
6.38
136.
4413
6.67
137.
8713
7.92
138.
1213
8.20
138.
7313
8.75
138.
8015
5.30
156.
2615
6.61
159.
4016
0.56
OBnO
OBnOBn
BnOBnO
BnO OMOM
OMOM
OBn OH
15bO
-
S48
1H NMR spectrum of Compound 16a (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
03.
542
3.54
83.
555
3.74
33.
755
3.80
33.
873
3.91
34.
003
4.10
74.
496
4.54
34.
571
4.58
54.
619
4.64
64.
725
4.88
84.
896
4.91
54.
941
4.94
84.
954
4.97
85.
308
5.31
75.
364
5.37
06.
532
6.63
56.
825
6.83
96.
844
6.89
27.
050
7.06
97.
186
7.19
87.
224
7.23
07.
257
7.26
57.
274
7.28
37.
293
7.29
77.
303
7.30
87.
312
7.32
17.
332
7.33
77.
967
7.98
6
7.09
77.
232
3.08
90.
610
0.43
65.
307
4.09
5
4.04
7
0.96
62.
000
19.5
91
1.01
6
OMeO
OMeOBn
BnOBnO
BnO OMOM
OMOM
16a
O
O
-
S49
13C NMR spectrum of Compound 16a (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.8
056
.31
56.5
156
.54
56.6
356
.65
63.4
564
.52
72.5
273
.21
73.3
973
.45
74.3
974
.96
75.2
575
.55
76.8
477
.16
77.4
878
.41
78.4
978
.90
79.0
080
.88
87.4
895
.13
95.2
695
.90
103.
2911
2.38
118.
3112
7.34
127.
3912
7.44
127.
5312
7.65
127.
7212
7.75
127.
7812
7.94
127.
9612
8.04
128.
1212
8.15
128.
3112
8.41
128.
4512
8.50
128.
5713
8.23
138.
4013
8.55
139.
1214
4.28
151.
4015
2.96
159.
4716
2.81
OMeO
OMeOBn
BnOBnO
BnO OMOM
OMOM
16a
O
O
-
S50
DEPT spectrum of Compound 16a (CDCl3, 100 MHz)
DEPT 135
DEPT 90
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13C NMR
-
S51
1H-1H COSY spectrum of Compound 16a (CDCl3)
-
S52
HSQC spectrum of Compound 16a (CDCl3)
-
S53
HMBC spectrum of Compound 16a (CDCl3)
-
S54
1H NMR spectrum of Compound 16b (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
03.
344
3.35
13.
375
3.56
23.
569
3.57
63.
583
4.29
64.
300
4.33
14.
417
4.42
24.
445
4.47
34.
682
4.75
74.
767
4.91
84.
924
4.92
74.
949
4.95
75.
116
5.15
55.
166
6.47
46.
729
6.74
66.
883
6.89
56.
901
7.00
87.
048
7.06
27.
067
7.08
17.
097
7.10
27.
110
7.12
67.
145
7.16
17.
168
7.17
87.
197
7.24
37.
262
7.36
87.
377
7.38
67.
551
7.56
97.
795
7.90
4
11.5
12
0.33
10.
697
5.17
2
12.8
53
1.00
02.
097
27.6
78
2.06
80.
317
0.69
9
OBnO
OBnOBnBnO
BnO
BnO OMOM
OMOM
16b
O
O
-
S55
13C NMR spectrum of Compound 16b (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
56.2
456
.30
56.3
556
.39
70.3
073
.32
73.8
274
.04
74.9
175
.21
76.8
477
.16
77.3
677
.48
78.1
678
.28
79.2
887
.81
95.0
295
.62
97.2
310
3.18
110.
1411
2.18
117.
0311
7.74
127.
0312
7.13
127.
2012
7.39
127.
4112
7.55
127.
5912
7.70
127.
8012
7.89
127.
9112
7.96
128.
0712
8.18
128.
2312
8.30
128.
3812
8.41
128.
5612
8.86
135.
6913
7.42
138.
1213
8.25
138.
7414
4.17
151.
2415
2.80
159.
1115
9.37
162.
4917
3.72
OBnO
OBnOBn
BnOBnO
BnO OMOM
OMOM
16b
O
O
-
S56
DEPT spectrum of Compound 16b (CDCl3, 100 MHz)
DEPT 135
DEPT 90
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
13C NMR
-
S57
1H-1H COSY spectrum of Compound 16b (CDCl3)
-
S58
HSQC spectrum of Compound 16b (CDCl3)
-
S59
HMBC spectrum of Compound 16b (CDCl3)
-
S60
1H NMR spectrum of Compound 17a (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
03.
440
3.54
83.
553
3.55
93.
785
3.87
83.
897
3.91
43.
993
4.03
34.
511
4.53
54.
616
4.72
74.
935
4.96
34.
974
4.97
85.
003
5.01
95.
160
5.29
15.
301
5.33
95.
385
6.24
56.
341
6.77
06.
788
6.80
36.
821
6.95
16.
972
6.99
17.
002
7.02
07.
148
7.17
87.
185
7.25
37.
271
7.28
77.
290
7.30
77.
316
7.32
77.
334
7.34
07.
357
7.36
17.
370
7.38
87.
926
7.93
6
6.01
08.
395
1.52
31.
522
0.53
00.
501
0.53
60.
521
4.06
48.
176
0.48
30.
513
2.00
5
19.7
27
1.03
3
OBnO
OBnOBn OBn
OMeO
OMe O
OMOM
OMOM
17a
-
S61
13C NMR spectrum of Compound 17a (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
55.8
756
.37
56.4
756
.51
56.6
256
.67
72.4
872
.77
73.2
573
.35
74.6
875
.15
75.2
876
.09
76.8
477
.16
77.3
677
.48
78.5
678
.62
79.6
279
.69
79.8
487
.88
87.9
890
.55
91.5
495
.29
96.0
710
3.48
112.
6212
7.41
127.
4712
7.49
127.
5212
7.77
127.
8612
7.87
127.
9212
7.94
128.
0212
8.11
128.
1712
8.22
128.
3012
8.37
128.
5312
8.57
128.
6213
7.82
138.
5913
8.62
138.
6613
8.77
138.
8213
8.86
144.
2416
2.40
OBnO
OBnOBn OBn
OMeO
OMe O
OMOM
OMOM
17a
-
S62
HSQC spectrum of Compound 17a (CDCl3)
-
S63
HMBC spectrum of Compound 17a (CDCl3)
-
S64
1H NMR spectrum of Compound 17b (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
03.
366
3.47
23.
478
3.49
33.
693
4.40
84.
439
4.49
04.
832
4.84
04.
904
4.95
45.
124
5.14
55.
150
5.16
95.
227
5.23
95.
274
6.27
86.
302
6.66
36.
861
6.89
27.
075
7.07
97.
114
7.12
07.
128
7.13
37.
145
7.15
07.
157
7.16
37.
173
7.18
97.
205
7.21
37.
216
7.22
67.
237
7.24
27.
247
7.28
07.
283
7.30
67.
318
7.32
27.
325
7.33
77.
356
7.53
27.
885
7.89
9
1.01
25.
231
5.11
61.
040
5.06
20.
428
0.65
611
.216
1.05
9
1.99
8
30.0
22
2.00
0
1.08
8
OBnO
OBnOBn OBn
OBnO
OBn O
OMOM
OMOM
17b
-
S65
13C NMR spectrum of Compound 17b (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
56.4
956
.53
56.6
456
.70
70.8
171
.12
71.3
072
.97
73.2
473
.61
74.4
474
.47
75.0
475
.59
76.8
477
.16
77.4
878
.46
79.2
379
.48
87.9
187
.95
95.2
795
.32
96.0
010
3.81
126.
9912
7.01
127.
1812
7.44
127.
4712
7.51
127.
6412
7.66
127.
7712
7.87
127.
9012
8.00
128.
0712
8.11
128.
1812
8.26
128.
3112
8.43
128.
4912
8.51
128.
5712
8.61
128.
6712
8.83
128.
8513
6.12
136.
5113
8.13
138.
3513
8.58
139.
0214
4.27
OBnO
OBnOBn OBn
OBnO
OBn O
OMOM
OMOM
17b
-
S66
HSQC spectrum of Compound 17b (CDCl3)
-
S67
HMBC spectrum of Compound 17b (CDCl3)
-
S68
1H NMR spectrum of Compound 18b (CDCl3, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.67
63.
700
4.36
24.
371
4.38
94.
395
4.42
84.
444
4.48
14.
692
4.71
94.
723
4.75
14.
760
4.78
84.
920
5.01
76.
017
6.04
06.
368
6.54
86.
764
6.78
16.
798
6.80
16.
851
6.85
46.
864
6.88
26.
894
6.98
66.
992
7.00
17.
010
7.02
67.
032
7.10
27.
120
7.13
07.
135
7.14
17.
144
7.15
17.
159
7.16
67.
174
7.19
57.
213
7.22
37.
228
7.28
77.
303
7.37
513
.396
13.5
11
0.55
00.
444
4.08
6
5.66
0
6.53
9
1.00
80.
540
0.46
0
27.8
98
0.90
3
0.46
30.
541
OBnO
OHOBn
BnOBnO
BnO OH
OH
18b
O
O
-
S69
13C NMR spectrum of Compound 18b (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
70.8
573
.54
73.6
974
.05
74.3
374
.89
75.1
775
.54
76.8
477
.16
77.4
878
.30
78.4
210
2.32
102.
4410
6.18
106.
2311
2.60
113.
0112
7.15
127.
3412
7.56
127.
6012
7.65
127.
8812
7.95
128.
1412
8.17
128.
3612
8.38
128.
4612
8.51
128.
5412
8.63
128.
6513
6.01
136.
0513
6.40
137.
7613
7.81
137.
9113
8.35
138.
5813
8.68
141.
3114
2.23
151.
4215
1.74
152.
8015
4.07
157.
4815
7.69
161.
3616
1.70
163.
3316
3.79
179.
0917
9.30
OBnO
OHOBn
BnOBnO
BnO OH
OH
18b
O
O
-
S70
1H NMR spectrum of Compound 19 (CDCl3, 400 MHz)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.64
53.
667
3.70
93.
712
3.73
64.
448
4.46
34.
491
4.54
64.
574
4.60
34.
623
4.74
64.
781
4.81
04.
837
4.85
34.
863
4.88
24.
952
4.96
74.
979
5.00
85.
016
5.04
85.
069
5.08
76.
542
7.11
37.
148
7.15
47.
168
7.18
87.
196
7.20
57.
210
7.21
47.
217
7.22
27.
232
7.24
67.
255
7.26
27.
266
7.27
07.
287
7.30
47.
318
7.32
47.
329
7.34
77.
367
7.47
012
.354
12.4
81
5.01
3
18.9
03
2.28
6
42.2
05
1.00
0
OBnO
OBnOBn
BnOBnO
BnO OBn
OH
OBn OH
O19
-
S71
13C NMR spectrum of Compound 19 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
70.5
971
.16
71.2
371
.48
73.4
873
.56
74.1
574
.41
75.0
175
.14
75.4
376
.84
77.1
677
.36
77.4
878
.24
78.3
279
.28
79.5
810
0.60
114.
6612
6.89
127.
0012
7.14
127.
2912
7.35
127.
4312
7.55
127.
6812
7.72
127.
7812
7.83
127.
9612
8.00
128.
0512
8.14
128.
3012
8.36
128.
4012
8.48
128.
5712
8.61
128.
6412
8.72
128.
7812
8.88
128.
9113
5.24
136.
3313
6.44
136.
7013
8.30
138.
4213
8.96
153.
1915
6.72
159.
0416
0.80
OBnO
OBnOBn
BnOBnO
BnO OBn
OH
OBn OH
O19
-
S72
1H NMR spectrum of Compound 23 (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
3.69
24.
433
4.46
04.
533
4.54
74.
562
4.57
74.
597
4.62
34.
673
4.68
54.
809
4.87
74.
888
5.04
65.
063
5.09
25.
199
5.21
55.
267
5.48
96.
574
6.58
56.
847
6.86
26.
881
7.01
47.
022
7.03
17.
055
7.12
07.
180
7.20
17.
221
7.23
47.
258
7.26
87.
296
7.31
47.
332
7.34
27.
351
7.36
27.
375
7.37
87.
393
7.41
27.
427
7.44
47.
462
7.50
07.
510
7.67
27.
690
7.73
7
5.14
7
20.7
88
0.89
8
1.00
0
39.8
25
OBnO
OBnOBn
BnOBnO
BnO OBn
OAllylO
23
O
-
S73
13C NMR spectrum of Compound 23 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
65.0
870
.02
70.4
671
.05
73.4
373
.95
74.1
575
.04
75.3
576
.84
77.1
677
.48
78.3
178
.54
79.4
087
.90
97.3
310
1.12
116.
2011
7.86
117.
9512
6.87
127.
1112
7.15
127.
2412
7.29
127.
4312
7.51
127.
7212
7.83
127.
8612
7.92
128.
0012
8.04
128.
2012
8.30
128.
3512
8.36
128.
4312
8.51
128.
5412
8.69
128.
7312
8.95
132.
8713
5.83
135.
9913
7.56
138.
2813
8.39
138.
8714
6.11
150.
8315
4.15
159.
1415
9.46
162.
5117
3.92
OBnO
OBnOBn
BnOBnO
BnO OBn
OAllylO
23
O
-
S74
1H NMR spectrum of Compound 24 (CDCl3, 400 MHz)
23456789101112 ppm
3.63
63.
647
3.65
84.
413
4.45
24.
544
4.57
34.
783
4.80
94.
857
4.86
65.
032
5.06
95.
181
5.19
16.
575
6.84
56.
865
7.01
67.
019
7.02
27.
027
7.03
57.
181
7.18
87.
215
7.21
97.
227
7.23
47.
242
7.24
67.
254
7.26
17.
266
7.27
27.
285
7.29
27.
296
7.29
87.
309
7.31
77.
320
7.32
67.
372
7.39
17.
395
7.40
87.
415
7.41
97.
422
7.50
47.
659
7.67
67.
705
7.79
4
2.03
13.
065
1.04
15.
090
10.5
49
0.95
9
0.97
33.
005
32.3
98
3.00
0
OBnO
OBnOBn
BnOBnO
BnO OBn
OHO
O
24
-
S75
13C NMR spectrum of Compound 24 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
70.6
571
.32
73.3
973
.90
74.1
374
.90
75.2
376
.84
77.1
677
.29
77.4
878
.28
78.4
579
.11
87.7
497
.35
99.6
310
9.85
110.
1211
6.66
117.
3512
7.23
127.
2812
7.44
127.
5312
7.65
127.
6812
7.79
127.
8712
7.96
128.
0212
8.09
128.
1212
8.17
128.
2612
8.30
128.
3512
8.38
128.
4512
8.52
128.
6712
9.31
135.
2613
5.91
137.
5713
7.97
138.
0713
8.20
138.
2413
8.34
138.
7914
3.27
149.
9015
1.57
159.
0015
9.35
162.
4817
3.90
OBnO
OBnOBn
BnOBnO
BnO OBn
OHO
O
24
-
S76
1H NMR spectrum of Compound 26 (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
1.79
91.
818
1.93
52.
007
2.01
82.
045
2.05
82.
086
3.65
93.
664
3.68
74.
243
4.47
14.
557
4.57
14.
864
4.87
45.
073
5.09
35.
101
5.13
25.
151
5.16
95.
181
5.19
05.
208
5.36
46.
616
6.83
86.
857
6.90
47.
027
7.04
77.
050
7.18
77.
227
7.23
17.
241
7.25
27.
261
7.27
27.
277
7.29
27.
317
7.32
67.
341
7.35
67.
371
7.39
07.
408
7.42
67.
449
7.58
67.
604
8.02
1
3.02
01.
002
1.00
92.
024
1.05
12.
039
2.08
8
6.34
4
8.64
6
14.8
15
0.96
93.
000
35.5
91
0.96
9
OO
BnO
OBn O
OBn
OOBn
BnOBnO
BnO
O
AcOOAc
OAc
OAc
26
-
S77
13C NMR spectrum of Compound 26 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.4
220
.70
20.7
462
.20
68.4
970
.53
71.0
571
.08
72.4
472
.80
73.5
173
.93
74.2
975
.12
75.4
776
.84
77.1
677
.48
78.3
178
.49
79.4
387
.95
100.
1011
3.60
127.
0712
7.08
127.
2612
7.41
127.
5512
7.60
127.
8012
7.93
128.
0012
8.07
128.
1212
8.22
128.
3712
8.43
128.
5012
8.52
128.
5912
8.62
128.
8012
8.84
135.
6613
5.81
137.
5813
8.26
138.
3013
8.39
138.
8614
4.18
154.
5915
9.16
169.
3216
9.58
170.
2417
1.19
OO
BnO
OBn O
OBn
OOBn
BnOBnO
BnO
O
AcOOAc
OAc
OAc
26
-
S78
1H NMR spectrum of Compound 27 (CDCl3, 400 MHz)
12 11 10 9 8 7 6 5 4 3 2 1 0 ppm
0.00
01.
684
1.70
91.
952
1.95
61.
979
1.99
32.
008
2.05
42.
080
2.14
32.
147
2.23
42.
336
2.41
02.
432
3.73
63.
755
3.90
73.
938
3.97
53.
984
3.99
24.
000
4.00
94.
015
4.15
94.
174
4.32
04.
329
4.35
14.
362
4.75
84.
781
5.00
85.
029
5.04
35.
052
5.07
25.
097
5.12
15.
157
5.16
65.
176
5.22
15.
247
5.25
95.
267
5.64
97.
087
7.11
87.
165
7.21
97.
697
7.72
5
3.02
018
.006
3.04
03.
445
6.03
0
1.00
21.
003
1.05
52.
002
1.04
51.
005
6.13
9
1.04
8
1.10
70.
969
1.00
0
OO
AcO
OAc O
OAc
OOAc
AcOAcO
AcO
O
AcO
OAcOAc
OAc
27
-
S79
13C NMR spectrum of Compound 27 (CDCl3, 100 MHz)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
20.3
820
.41
20.6
020
.63
20.7
020
.74
20.7
721
.27
21.4
061
.87
61.9
762
.04
67.9
968
.19
68.3
570
.33
70.5
372
.41
72.4
772
.54
74.4
074
.56
76.5
776
.68
76.8
477
.16
77.3
677
.48
98.3
711
0.00
110.
4111
0.58
111.
8111
2.11
112.
7711
2.86
118.
2012
0.37
145.
9514
6.06
149.
4915
0.80
150.
8815
4.22
157.
3516
7.72
168.
0116
8.06
168.
2116
9.53
169.
6016
9.65
169.
8617
0.03
170.
2817
0.46
170.
8717
3.63
OO
AcO
OAc O
OAc
OOAc
AcOAcO
AcO
O
AcO
OAcOAc
OAc
27
-
S80
1H NMR spectrum data for natural and synthetic Mangifein
Assignments
Natural
Mangiferin
Synthetic
Mangiferin
DMSO-d6
400 MHz
DMSO-d6
400 MHz
HO-1 13.70(s) 13.75 (s, 1H)
HO-6 10.70(s)
10.53 (br s, 3H) HO-3 10.60(s)
HO-7 9.78(s)
H-8 7.35(s) 7.38(s, 1H)
H-5 6.83(s) 6.86 (s, 1H)
H-4 6.34(s) 6.37 (s, 1H)
H-1' 4.60(d, J = 9.6 Hz) 4.59 (d, J = 9.6 Hz,
1H)
-
S81
13C NMR spectrum data for natural and synthetic Mangifein
Assignments
Natural
Mangiferin
Synthetic
Mangiferin Assignments
Natural
Mangiferin
Synthetic
Mangiferin
DMSO-d6
100 MHz
DMSO-d6
100 MHz
DMSO-d6
100 MHz
DMSO-d6
100 MHz
1 162.5 162.1 C-1' 73.8 73.5
2 108.3 107.7 C-2' 71.3 70.9
3 164.5 164.1 C-3' 79.7 79.3
4 94.0 93.8 C-4' 70.9 70.7
4a 156.9 156.6 C-5' 82.3 81.7
5 103.3 103.0 C-6' 62.2 61.8
6 154.7 154.2
7 144.4 143.9
8 112.4 112.1
8a 108.7 108.4
9 179.8 179.4
9a 102.0 101.7
10a 151.4 151.1
-
S82
1H NMR spectrum data for natural and synthetic Homomangifein
Assignments
Natural
Homomangiferin
Synthetic
Homomangiferin
DMSO-d6
400 MHz
DMSO-d6 + D2O
400 MHz
HO-1 13.66(s) 13.66/13.65(s)
H-8 7.39(s) 7.39/7.38(s)
H-5 6.88(s) 6.89(s)
H-4 6.66(s) 6.62/6.61(s)
H-1' 4.57(d) 4.61/4.56(d)
H-3' 3.98(m) 4.19/3.98(t)
H-6' 3.70/3.33(m) 3.35(m)
H-5' 3.16(m)
3.23-3.02(m) H-2' 3.10(m)
H-4' 3.07(m)
CH3O 3.88(s) 3.86/3.84(s)
-
S83
13C NMR spectrum data for natural and synthetic Homomangifein
Assignments
Natural
Homomangiferin
Synthetic
HomomangiferinAssignments
Natural
Homomangiferin
Synthetic
Homomangiferin
DMSO-d6
100 MHz
DMSO-d6 + D2O
100 MHz
DMSO-d6
100 MHz
DMSO-d6 + D2O
100 MHz
1 161.8 161.3/160.6 C-1' 73.1 73.1/72.9
2 108.9 108.3 C-2' 82.2 82.0/81.8
3 164.7 165.7/164.5 C-3' 70.8 70.5/69.9
4 90.2 91.0/90.2 C-4' 71.4 71.0
4a 157.3 157.2/157.1 C-5' 79.6 79.1
5 103.0 102.9 C-6' 62.2 61.8
6 154.7 154.4 CH3O 56.7 56.8/56.5
7 144.4 144.1
8 108.5 108.6
8a 112.3 112.2
9 179.6 179.7/179.4
9a 102.3 102.6/102.2
10a 151.4 151.2
-
S84
1H NMR spectrum data for natural and synthetic Neomangifein
Assignments
Natural
Neomangiferin
Synthetic
Neomangiferin
DMSO-d6
400 MHz
DMSO-d6 + D2O
400 MHz
H-4 6.37(s) 6.41(s)
H-5 6.93(s) 6.96(s)
H-8 7.69(s) 7.70(s)
2-Glc, H-1' 4.57(d) 4.59(d)
7-Glc, H-1" 4.87(d) 4.91(d)
-
S85
13C NMR spectrum data for natural and synthetic Neomangifein
Assignments
Natural
Neomangiferin
Synthetic
Neomangiferin Assignments
Natural
Neomangiferin
Synthetic
Neomangiferin
DMSO-d6
100 MHz
DMSO-d6
100 MHz
DMSO-d6
100 MHz
DMSO-d6
100 MHz
1 162.5 161.7 2-Glc
2 108.3 107.9 C-1' 73.8 73.4
3 164.5 164.2 C-2' 71.3 70.7
4 94.0 93.8 C-3' 79.7 79.0
4a 154.7 155.0 C-4' 71.0 70.4
5 103.3 102.1 C-5' 82.2 81.7
6 156.9 156.5 C-6' 61.4 61.6
7 144.4 143.7 (7-Glc)C-1" 103.4 103.4
8 112.4 112.0 C-2" 73.5 73.3
8a 108.8 110.5 C-3" 76.1 75.9
9 179.8 179.2 C-4" 69.6 69.7
9a 102.0 101.5 C-5" 77.3 77.3
10a 151.5 152.8 C-6" 60.7 60.7
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