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Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008
S1
Chemoenzymatic Syntheses of Tumor-Associated Carbohydrate Antigen Globo-H and Stage-Specific
Embryonic Antigen 4
Supporting Information
Zhen Wang,a Michel Gilbert,b Hironobu Eguchi,c Hai Yu,d Jiansong Cheng,d Saddam Muthana,d Luyuan Zhou,a Peng George Wang,c
Xi Chen,d and Xuefei Huang a* aDepartment of Chemistry, The University of Toledo, 2801 W. Bancroft Street, MS 602, Toledo, Ohio 43606 USA bNational Research Council Canada, Institute for Biological Sciences, Glycobiology Program, 100 Sussex Drive, Ottawa, ON K1A
0R6 Canada cThe Ohio State University, Departments of Biochemistry and Chemistry, 484 West 12th Avenue, Columbus, OH 43210 USA dDepartment of Chemistry, University of California, One Shields Avenue, Davis, CA USA
Table of content General experimental procedures S7
Analytical data for compounds S8
1H-NMR of compound 5 (600 MHz, CDCl3) S15
S2
13C-NMR of compound 5 (150 MHz, CDCl3) S16
1H–1H gCOSY of compound 5 (600 MHz, CDCl3) S17
1H–13C gHMQC of compound 5 (600 MHz, CDCl3) S18
1H–13C gHMQC (without 1H decoupling) of compound 5 (600 MHz, CDCl3) S19
1H–13C gHMQC (without 1H decoupling) of compound 5 (enlarged) (600 MHz, CDCl3) S20
1H-NMR of compound 4α (600 MHz, CDCl3) S21
13C-NMR of compound 4α (150 MHz, CDCl3) S22
1H–1H gCOSY of compound 4α (600 MHz, CDCl3) S23
1H–13C gHMQC of compound 4α (600 MHz, CDCl3) S24
1H–13C gHMQC (without 1H decoupling) of compound 4α (600 MHz, CDCl3) S25
1H–13C gHMQC (without 1H decoupling) of compound 4α (enlarged) (600 MHz, CDCl3) S26
1H-NMR of compound 4β (600 MHz, CDCl3) S27
13C-NMR of compound 4β (150 MHz, CDCl3) S28
1H–1H gCOSY of compound 4β (600 MHz, CDCl3) S29
1H–13C gHMQC of compound 4β (600 MHz, CDCl3) S30
S3
1H–13C gHMQC (without 1H decoupling) of compound 4β (600 MHz, CDCl3) S31
1H–13C gHMQC (without 1H decoupling) of compound 4β (enlarged) (600 MHz, CDCl3) S32
1H-NMR of compound 3 (600 MHz, D2O) S33
13C-NMR of compound 3 (150 MHz, D2O) S34
1H–1H gCOSY of compound 3 (600 MHz, D2O) S35
1H–13C gHMQC of compound 3 (600 MHz, D2O) S36
1H–13C gHMQC of compound 3 (enlarged) (600 MHz, D2O) S37
1H–13C gHMQC (without 1H decoupling) of compound 3 (600 MHz, D2O) S38
1H–13C gHMQC (without 1H decoupling) of compound 3 (enlarged) (600 MHz, D2O) S39
1H-NMR of compound 11 (600 MHz, CDCl3) S40
13C-NMR of compound 11 (150 MHz, CDCl3) S41
1H–1H gCOSY of compound 11 (600 MHz, CDCl3) S42
1H–13C gHMQC of compound 11 (600 MHz, CDCl3) S43
1H–13C gHMQC (without 1H decoupling) of compound 11 (600 MHz, CDCl3) S44
1H–13C gHMQC (without 1H decoupling) of compound 11 (enlarged) (600 MHz, CDCl3) S45
1H-NMR of compound 12 (600 MHz, CDCl3) S46
S4
13C-NMR of compound 12 (150 MHz, CDCl3) S47
1H–1H gCOSY of compound 12 (600 MHz, CDCl3) S48
1H–13C gHMQC of compound 12 (600 MHz, CDCl3) S49
1H–13C gHMQC (without 1H decoupling) of compound 12 (600 MHz, CDCl3) S50
1H–13C gHMQC (without 1H decoupling) of compound 12 (enlarged) (600 MHz, CDCl3) S51
1H-NMR of compound 13 (600 MHz, CDCl3) S52
13C-NMR of compound 13 (150 MHz, CDCl3) S53
1H–1H gCOSY of compound 13 (600 MHz, CDCl3) S54
1H–13C gHMQC of compound 13 (600 MHz, CDCl3) S55
1H–13C gHMQC (without 1H decoupling) of compound 13 (600 MHz, CDCl3) S56
1H–13C gHMQC (without 1H decoupling) of compound 13 (enlarged) (600 MHz, CDCl3) S57
1H-NMR of compound 17α (600 MHz, CDCl3) S58
13C-NMR of compound 17α (150 MHz, CDCl3) S59
1H–1H gCOSY of compound 17α (600 MHz, CDCl3) S60
1H–13C gHMQC (without 1H decoupling) of compound 17α (600 MHz, CDCl3) S61
S5
1H–13C gHMQC (without 1H decoupling) of compound 17α (enlarged) (600 MHz, CDCl3) S62
1H-NMR of compound 19 (600 MHz, CDCl3) S63
13C-NMR of compound 19 (150 MHz, CDCl3) S64
1H–1H gCOSY of compound 19 (600 MHz, CDCl3) S65
1H-NMR of compound 20α (600 MHz, CDCl3) S66
13C-NMR of compound 20α (150 MHz, CDCl3) S67
1H–1H gCOSY of compound 20α (600 MHz, CDCl3) S68
1H–13C gHMQC of compound 20α (600 MHz, CDCl3) S69
1H–13C gHMQC (without 1H decoupling) of compound 20α (600 MHz, CDCl3) S70
1H–13C gHMQC (without 1H decoupling) of compound 20α (enlarged) (600 MHz, CDCl3) S71
1H-NMR of compound 2b (600 MHz, D2O) S72
13C-NMR of compound 2b (150 MHz, D2O) S73
1H–1H gCOSY of compound 2b (600 MHz, D2O) S74
1H–13C gHMQC of compound 2b (600 MHz, D2O) S75
1H–13C gHMQC of compound 2b (enlarged) (600 MHz, D2O) S76
S6
1H–13C gHMQC (without 1H decoupling) of compound 2b (600 MHz, D2O) S77
1H–13C gHMQC (without 1H decoupling) of compound 2b (enlarged) (600 MHz, D2O) S78
1H-NMR of compound 23 (600 MHz, D2O) S79
13C-NMR of compound 23 (150 MHz, D2O) S80
1H–1H gCOSY of compound 23 (600 MHz, D2O) S81
1H–13C gHMQC of compound 23 (600 MHz, D2O) S82
1H–13C gHMQC of compound 23 (enlarged) (600 MHz, D2O) S83
1H–13C gHMQC (without 1H decoupling) of compound 23 (600 MHz, D2O) S84
1H–13C gHMQC (without 1H decoupling) of compound 23 (enlarged) (600 MHz, D2O) S85
1H-NMR of compound S1 (600 MHz, CDCl3) S86
13C-NMR of compound S1 (150 MHz, CDCl3) S87
1H–1H gCOSY of compound S1 (600 MHz, CDCl3) S88
1H–13C gHMQC of compound S1 (600 MHz, CDCl3) S89
1H–13C gHMQC (without 1H decoupling) of compound S1 (600 MHz, CDCl3) S90
1H–13C gHMQC (without 1H decoupling) of compound S1 (enlarged) (600 MHz, CDCl3) S91
S7
General Experimental Procedures. All reactions were carried out under nitrogen with anhydrous solvents in flame-dried glassware,
unless otherwise noted. All glycosylation reactions were performed in the presence of molecular sieves, which were flame-dried right
before the reaction under high vacuum. Glycosylation solvents were dried using an solvent purification system and used directly
without further drying. Chemicals used were reagent grade as supplied except where noted. Analytical thin-layer chromatography was
performed using silica gel 60 F254 glass plates; Compound spots were visualized by UV light (254 nm) and by staining with a yellow
solution containing Ce(NH4)2(NO3)6 (0.5 g) and (NH4)6Mo7O24 4H2O (24.0 g) in 6% H2SO4 (500 mL). Flash column chromatography
was performed on silica gel 60 (230–400 Mesh). NMR spectra were referenced using Me4Si (0 ppm), residual CHCl3 (δ 1H-NMR
7.26 ppm, 13C-NMR 77.0 ppm). Peak and coupling constant assignments are based on 1H-NMR, 1H–1H gCOSY and (or) 1H–13C
gHMQC and 1H–13C gHMBC experiments. All optical rotations were measured at 25 °C using the sodium D line. ESI mass spectra
were recorded in positive ion mode. High-resolution mass spectra were recorded on a Micromass electrospray mass spectrometer
equipped with an orthogonal electrospray source (Z-spray) operated in positive ion mode.
3-Aminopropyl 5-acetamido-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonic acid-(2→3)-β-D-galactopyranosyl-
(1→3)-2-acetamido-2-deoxy-β-D-galactopyranosyl-(1→3)-α-D-galactopyranosyl-(1→4)-β-D-galactopyranosyl-(1→4)-β-D-
glucopyranoside (2b). [α]25D +32.6 (c = 0.38, D2O); 1H-NMR (600 MHz, D2O): δ 1.58 (t, 1H, J = 12 Hz), 1.74 (s, 6H), 1.80-1.82 (m,
5H), 2.54-2.56 (dd, 1H, J = 3.6, 12 Hz), 2.96 (t, 2H, J = 6.6 Hz), 3.12 (m, 1H), 3.33-3.88 (m, 31H), 3.97 (s, 1H), 4.05 (s, 1H), 4.17-
S8
4.20 (m, 1H), 4.30-4.32 (m, 3H), 4.49 (d, 1H, J = 9 Hz), 4.63-4.71 (m, 1H); 13C-NMR (150 MHz, D2O): δ 22.1, 22.4 (×2), 26.8, 37.7,
39.8, 51.4, 51.7, 60.1, 60.4, 61.1, 62.6, 67.4, 67.7, 67.9, 68.1, 68.5, 69.0, 69.1, 70.4, 71.0, 71.9, 72.2, 72.9 (×2), 74.5, 74.7, 74.9 (×2),
75.6 (×2), 77.2, 78.8 (×2), 79.9, 99.7, 100.5, 102.1, 103.1, 103.4, 104.7, 174.1, 175.1, 175.2, 181.5; gHMQC (without 1H decoupling): 1J13C,1H = 171.0 Hz, 163.8 Hz, 161.5 Hz, 161.2 Hz, 160.4 Hz; HRMS: [M+Na]+ C46H79N3O34 calcd 1240.4443, obsd 1240.4366.
3-Aminopropyl β-D-galactopyranosyl-(1→3)-2-acetamido-2-deoxy-β-D-galactopyranosyl-(1→3)-α-D-galactopyranosyl-(1→4)-
β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside (3). [α]25D +240 (c = 1, H2O); 1H-NMR (600 MHz, D2O): δ 1.74 (s, 3H), 1.83
(m, 2H), 1.86 (s, 3H), 2.94 (t, 2H, J = 7.2 Hz), 3.12 (m, 1H), 3.34-3.90 (m, 29H), 4.01 (d, 1H, J = 3.0 Hz), 4.08 (d, 1H, J = 2.4 Hz),
4.20-4.23 (m, 1H), 4.28 (d, 1H, J = 7.8 Hz), 4.34 (d, 2H, J = 7.8 Hz), 4.52 (d, 1H, J = 8.4 Hz), 4.74 (d, 1H, J = 3.6 Hz); 13C-NMR
(150 MHz, D2O): δ 22.5, 23.4, 27.4, 37.7, 51.6, 60.1, 60.5, 60.6, 61.2, 67.8, 68.1, 68.7, 69.1, 70.4, 70.8, 71.0, 72.3, 72.6, 73.0, 74.6,
74.8, 75.0, 75.2, 75.6, 77.3, 78.9, 79.8, 89.5, 100.5, 102.2, 103.1, 103.5, 105.0, 175.2, 181.7; gHMQC (without 1H decoupling):
gHMQC (without 1H decoupling): 1JC1”,H1” = 170.5 Hz, other four 1JC1,H1 = 158.0, 161.9 Hz, 162.0, 162.0 Hz; HRMS: [M+Na]+
C35H62N2NaO26 calcd 949.3489, obsd 949.3462.
3-Azidopropyl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1→3)-4,6-benzylidene-2-(2,2,2-tri-chloroethoxycarbonylamino)-2-
deoxy-β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-benzyl-α-D-galactopyranosyl-(1→4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-
(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (4α): [α]25D +21.3 (c = 1, CH2Cl2); 1H-NMR (600 MHz, CDCl3): δ 1.84 (m, 2H,
OCH2CH2CH2N3), 2.66 (s, 1H), 3.19 (m, 1H), 3.25-3.28 (m, 2H), 3.30-3.38 (m, 6H), 3.44-3.68 (m, 10H), 3.66-3.83 (m, 6H), 3.92-
4.08 (m, 10H), 4.16-4.35 (m, 10H), 4.41-4.49 (m, 5H), 4.45-4.91 (m, 15H), 4.95 (d, 1H, J1’’,2’’ = 3.6 Hz, H-1’’), 5.02 (d, 1H, J = 11.4
Hz), 5.09 (d, 1H, J =12 Hz), 5.42 (s, 1H), 7.09-7.42 (m, 70H, aromatic); 13C-NMR (150 MHz, CDCl3): δ 29.2, 48.3, 54.0, 65.9, 66.4,
S9
67.6, 67.9, 68.1, 68.9 (×2), 69.3, 71.8, 72.9, 73.0, 73.1, 73.3, 73.5 (×2), 73.8, 74.1, 74.3, 74.6, 74.7, 74.8, 75.0 (×2), 75.2, 76.4, 76.7,
78.4, 79.4, 81.3, 81.5, 81.8, 81.5, 81.9, 100.6, 101.8, 102.7, 103.4, 104.5, 126.4, 126.9, 127.1, 127.3, 127.4 (×3), 127.5 (×4), 127.6
(×3), 127.7 (×2), 127.8 (×2), 127.9 (×3), 128.1 (×2), 128.2 (×4), 128.3 (×2), 128.4 (×3), 128.5, 129.4, 137.8, 138.1 (×2), 138.2, 138.3,
138.5, 138.6, 138.7, 138.8, 139.0, 139.4, 139.5, 153.7; HRMS: [M+Na]+ C134H141Cl3N4NaO27 calcd 2368.8774, obsd 2368.8848.
gHMQC (without 1H decoupling): 1JC1”,H1” = 169.0 Hz, other four 1JC1,H1 = 160.7 Hz, 160.7 Hz, 162.4, 162.4 Hz.
3-Azidopropyl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1→3)-4,6-benzylidene-2-(2,2,2-tri-chloroethoxycarbonylamino)-2-
deoxy-β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-benzyl-β-D-galactopyranosyl-(1→4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-
(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (4β): [α]25D +16.6 (c = 0.63, CH2Cl2); 1H-NMR (600 MHz, CDCl3): δ 1.85 (m, 2H,
OCH2CH2CH2N3), 3.24-3.41 (m, 10H), 3.45-3.63 (m, 12H), 3.69-3.78 (m, 7H), 3.87-3.95 (m, 5H), 4.06-4.56 (m, 17H), 4.56-4.81 (m,
11H), 4.87-4.96 (m, 4H), 5.06 (d, 1H, J = 11.4 Hz), 5.14 (d, 1H, J = 12 Hz), 5.51 (s, 1H), 6.96-7.50 (m, 70H, aromatic); 13C-NMR
(150 MHz, CDCl3): δ 29.2, 48.3, 65.9, 66.3, 66.4, 68.0, 68.7, 68.9, 69.0, 69.8, 72.5, 73.1, 73.2, 73.3 (×2), 73.4 (×2), 73.7, 73.8, 74.4,
74.6, 74.8, 75.1, 75.6, 76.0, 76.4, 78.9, 79.5, 80.3, 81.0, 81.6, 81.8, 82.3, 83.0, 100.6, 101.0, 102.6, 102.8, 103.5, 104.7, 126.3, 126.7,
127.0, 127.1 (×2), 127.2, 127.3, 127.4 (×2), 127.5 (×2), 127.6 (×3), 127.7 (×2), 127.8 (×2), 127.9, 128.0 (×3), 128.1, 128.2 (×2), 128.3
128.4 (×3), 128.7, 129.1, 138.0, 138.1, 138.2, 138.3, 138.5, 138.6 (×2), 138.7, 138.8, 139.1, 139.6, 139.7, 153.6; HRMS: [M+Na]+
C134H141Cl3N4NaO27 calcd 2367.8750, obsd 2367.8789. gHMQC (without 1H decoupling): five 1JC1,H1 = 159.2, 161.4, 162.8, 162.8,
163.8 Hz.
p-Tolyl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1→3)-4,6-benzylidene-2-(2,2,2-tri-chloroethoxycarbonylamino)-2-deoxy-
1-thio-β-D-galactopyranoside (5). [α]25D –6.8 (c = 1, CH2Cl2); 1H-NMR (600 MHz, CDCl3): δ 2.29 (s, 3H, SPhCH3), 3.38-3.41 (m,
3H, H-2, H-3’, H-5), 3.44-3.49 (m, 2H, H-5’, 6a’), 3.54-3.57 (m, 1H, H-6b’), 3.77-3.80 (m, 2H, , H-2’, H-4’), 3.85 (d, 1H, J = 12.0
S10
Hz, CH2Ph), 4.25-4.28 (m, 2H, H-3, H-6a), 4.34 (d, 1H, J6a,6b = 10.2 Hz, H-6b), 4.39-4.43 (m, 2H, H-4, CH2Ph), 4.45 (d, 1H, J1,2 = 7.8
Hz, H-1’), 4.52-4.58 (m, 3H, CH2CCl3, CH2Ph), 4.65-4.78 (m, 4H, CH2Ph), 4.90 (d, 1H, J = 12 Hz, CH2Ph), 4.96 (d, 1H, JNH,2 = 7.2
Hz, NH), 5.20 (d, 1H, J1,2 = 9.6 Hz), 5.45 (s, 1H, CHPh), 6.95-6.98 (m, 2H), 7.15-7.20 (m, 3H, aromatic), 7.23-7.36 (m, 20H,
aromatic), 7.45-7.48 (m, 4H, aromatic); 13C-NMR (150 MHz, CDCl3): δ 21.1, 51.8, 68.8, 69.1, 69.9, 73.0, 73.4 (×2), 73.6, 73.9, 74.5,
75.5, 75.8, 76.8, 77.0, 77.2, 79.4, 81.9, 100.4, 104.1, 126.4, 127.2, 127.4, 127.5 (×2), 127.6, 127.7, 127.8, 127.9, 128.1, 128.0, 128.1
(×2), 128.3 (×2), 128.4, 128.7, 129.5, 133.5, 137.7, 138.1, 138.3, 138.4, 139.1, 153.5; ESI-MS [M+Na]+ C57H58Cl3NNaO11S calcd
1092.3, obsd 1092.8.
p-Tolyl 3,4,6-tri-O-acetyl-2-(2,2,2-tri-chloroethoxycarbonylamino)-2-deoxy-β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-benzyl-1-
thio-β-D-galactopyranoside (11). 1H-NMR (600 MHz, CDCl3): δ 1.92, 2.02, 2.14 (3s, 9H, 3 × COCH3 ), 2.31 (s, 3H, SPhCH3), 3.60-
3.68 (m, 3H, H-5, H-6a, H-6b), 3.76 (t, 1H, H-5’), 3.84-3.96 (m, 4H, H-2, H-3, H-4, H-2’), 4.10-4.16 (m, 2H, H-6a’, H-6b’), 4.22 (d,
1H, JNH,2 = 9.6 Hz, NH), 4.40-4.48 (m, 4H, 2CH2CCl3, 2CH2Ph), 4.54-4.62 (m, 4H, 2CH2Ph, H-1, H-3’), 4.72 (d, 1H, J1,2 = 8.4 Hz, H-
1’), 4.98 (d, 1H, J = 11.4 Hz, CH2Ph), 5.12 (d, 1H, J = 11.4 Hz, CH2Ph), 5.28 (d, 1H, J3’,4’ = 2.4 Hz, H-4’), 6.96-7.46 (m, 19H,
aromatic); 13C-NMR (150 MHz, CDCl3): δ 20.8, 20.9, 21.0, 21.4, 52.8, 61.4, 66.7, 69.1, 70.1, 70.9, 73.8, 74.5, 74.6, 75.4, 75.9, 77.8,
78.7, 81.6, 88.0, 95.6, 102.1, 127.4, 127.5, 127.6, 128.0, 128.1, 128.2, 128.3 (×3), 128.6, 128.7, 129.0, 130.0, 130.1, 132.0, 137.6,
138.1, 138.9, 139.2, 154.4, 170.4 (×2), 170.6; 1JC1,H1 = 157.9 Hz, 1JC1’,H1’ = 161.8 Hz; HRMS: [M+Na]+ C49H54Cl3NNaO14S calcd
1040.2223, obsd 1040.2227.
p-Tolyl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1→3)-4,6-benzylidene-2-(2,2,2-tri-chloroethoxycarbonylamino)-2-deoxy-
β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside (12). 1H-NMR (600 MHz, CDCl3): δ 2.29 (s, 3H,
SPhCH3), 3.29 (s, 1H), 3.38-3.40 (m, 1H), 3.44-3.46 (m, 1H), 3.49-3.56 (m, 4H), 3.60-3.66 (m, 3H), 3.76-3.79 (m, 1H), 3.81-3.82 (m,
S11
3H), 3.92-3.94 (m, 1H), 4.11-4.12 (m, 1H), 4.20-4.22 (m, 2H), 4.33 (d, 1H, J1”,2” = 7.8 Hz, H-1”), 4.36-4.44 (m, 4H), 4.54-4.60 (m,
5H), 4.57 (d, 1H, J1,2 = 7.2 Hz, H-1), 4.66-4.80 (m, 5H), 4.90 (d, 1H, J = 11.4 Hz), 5.00 (d, 1H, J1’,2’ = 8.4 Hz, H-1’), 5.08 (d, 1H, J =
12 Hz), 5.51 (s, 1H, CHPh), 6.97 (d, 2H, J = 8.4 Hz), 7.16-7.35 (m, 36H, aromatic), 7.40-7.44 (m, 4H), 7.50-7.52 (m, 2H). 13C-NMR
(150 MHz, CDCl3): δ 21.1, 54.4, 66.4, 68.8, 69.0, 69.1, 73.2, 73.4 (×2), 73.5, 73.6, 74.3, 74.6, 74.8, 74.9, 75.5, 76.1, 77.4, 79.1, 81.9,
82.9, 87.7, 100.5, 101.0, 104.7, 126.3, 126.9, 127.2 (×2), 127.4, 127.5 (×2), 127.6, 127.7 (×2), 127.8 (×2), 127.9 (×2), 128.0, 128.1,
128.2, 128.3, 128.5, 128.7, 129.6, 130.1, 131.8, 137.1, 137.8, 138.0, 138.1, 138.4 (×2), 139.0, 139.1, 139.3, 153.7; 1JC1,H1 = 159.2 Hz, 1JC1’,H1’ = 163.3 Hz, 1JC1”,H1” = 161.1 Hz; ESI-MS [M+Na]+ C84H86Cl3NNaO16S calcd 1524.5, obsd 1524.9.
3-Azidopropyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1→2)-3,4,6-tri-O-benzyl-β-D-galactopyranosyl-(1→3)-4,6-benzylidene-2-
(2,2,2-tri-chloroethoxycarbonylamino)-2-deoxy-β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside
(13). 1H-NMR (600 MHz, CDCl3): δ 0.74 (d, 3H, J = 6.0 Hz), 2.29 (s, 3H, SPhCH3), 3.31 (s, 1H), 3.46-3.76 (m, 8H), 3.81-4.02 (m,
8H), 4.11-4.28 (m, 5H), 4.34-4.53 (m, 8H), 4.55-4.70 (m, 9H), 4.75-4.88 (m, 4H), 5.05 (b, 1H), 5.18 (d, 1H, J = 11.4 Hz), 5.38 (b,
1H), 5.52 (s, 1H, CHPh), 5.63 (d, 1H, J = 3.0 Hz), 6.96-7.44 (m, 54H, aromatic); 13C-NMR (150 MHz, CDCl3): δ 16.5, 21.3, 23.5,
24.9, 36.8, 54.8, 66.7, 67.1, 68.9, 69.2, 69.4, 72.3, 72.6, 72.7, 72.9, 73.7 (×2), 73.8 (×2), 74.0, 74.7, 74.8, 75.0, 75.7, 76.2, 77.7, 78.0,
78.1, 79.5, 83.7, 88.2, 97.2, 101.4, 101.8, 103.2, 126.8 (×2), 127.1, 127.2 (×2), 127.3 (×2), 127.5, 127.7, 127.9 (×2), 128.1, 128.2 (×3),
128.3 (×2), 128.4 (×3), 128.5, 128.6 (×2), 128.7, 129.1, 129.8, 130.5, 132.0, 137.4, 138.0, 138.2 (×2), 138.3, 138.5, 138.8, 139.1,
139.3, 139.4, 154.1; gHMQC (without 1H decoupling): 1JC1”’,H1”’ = 170.2 Hz, other three 1JC1,H1 = 161.2 Hz, 159.5 Hz, 159.5 Hz; ESI-
MS [M+Na]+ C104H108Cl3NNaO20S calcd 1850.6, obsd 1850.2.
S12
3-Azidopropyl 3,4,6-tri-O-acetyl-2-(2,2,2-tri-chloroethoxycarbonylamino)-2-deoxy-β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-
benzyl-α-D-galactopyranosyl-(1→4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1→3)-2,4,6-tri-O-benzyl-β-D-glucopyranoside
(17α). [α]25D +11.5 (c = 1, CH2Cl2); 1H-NMR (600 MHz, CDCl3): δ 1.85 (m, 2H, OCH2CH2CH2N3), 1.92, 1.92, 2.04 (3s, 9H, 3 ×
COCH3), 3.02 (t, 1H), 3.10 (m, 1H), 3.24-3.32 (m, 4H), 3.35 (t, 2H), 3.43-3.50 (m, 2H), 3.56-3.60 (m, 3H), 3.56 (d, 1H), 3.81-4.03
(m, 15H), 4.16 (d, 2H), 4.25-4.34 (m, 7H), 4.43-4.45 (m, 2H), 4.48 (d, 1H), 4.40 (d, 1H), 4.59-4.67 (m, 4H), 4.67-4.74 (m, 5H), 4.82
(d, 1H), 4.88 (d, 1H), 5.03-5.06 (m, 2H), 7.06-7.45 (m, 45H, aromatic); 13C-NMR (150 MHz, CDCl3): δ 20.8, 29.5, 48.5, 52.6, 61.2,
66.4, 66.7, 67.6, 67.7, 68.2, 69.6, 70.1, 70.7, 72.2, 73.0, 73.3, 73.7, 74.5, 75.1, 75.3, 75.4, 75.5, 76.7, 77.2, 77.3, 77.5, 79.7, 79.8, 81.7
(×2), 82.7, 100.8, 102.6, 102.7, 103.8, 127.6, 127.7, 127.8 (×2), 127.9 (×2), 128.0 (×3), 128.2 (×2), 128.3, 128.4, 128.5 (×4), 128.7,
129.0, 129.1, 130.1, 130.2, 138.2, 138.4, 138.5, 138.6, 138.7 (×2), 138.9, 139.3, 139.3, 154.4, 170.4 (×2), 170.5; 1JC1’’,H1’’ = 169.5 Hz,
other three 1JC1,H1 = 160.0 Hz, 163.0 Hz, 163.0 Hz; HRMS: [M+Na]+ C99H109Cl3N4NaO25 calcd 1883.6349, obsd 1883.6442.
p-Tolyl 2,4,6-tri-O-benzyl-3-O-p-nitrobenzoyl-1-thio-β-D-galactopyranoside (19). [α]25D +76.2 (c = 3, CH2Cl2); 1H-NMR
(600 MHz, CDCl3): δ 2.34 (s, 3H, SPhCH3), 3.70 (d, 2H, J = 6.6 Hz, H-6a, H-6b), 3.82 (t, 1H, J = 6.6 Hz, H-5), 4.08 (t, 1H, J1,2 = 9.6
Hz, H-2), 4.16 (d, 1H, J = 3.0 Hz, H-4), 4.45-4.58 (m, 5H), 4.70 (d, 1H, J1,2 = 9.6 Hz, H-1), 4.86 (d, 1H, J = 11.4 Hz), 5.23 (dd, 1H, J
= 3.0, 9.6 Hz, H-3), 7.03-7.08 (m, 2H), 7.11-7.12 (m, 5H), 7.17-7.24 (m, 5H), 7.27-7.34 (m, 5H), 7.48-7.53 (m, 2H), 7.93-7.94 (m,
2H), 8.17-8.18 (m, 2H); 13C-NMR (150 MHz, CDCl3): δ 21.4, 68.2, 73.8, 74.9, 75.2, 75.5, 75.6, 77.1,78.3, 88.3, 123.7, 127.8, 127.9,
128.0, 128.1, 128.2, 128.3, 128.5 (×2), 128.7, 130.0, 131.0, 132.5, 135.1, 137.9 (×3), 138.3, 150.8, 164.0; ESI-MS [M+Na]+
C41H39NNaO8S calcd 705.2, obsd 705.3.
3-Azidopropyl 2,4,6-tri-O-benzyl-3-O-p-nitrobenzoyl-α-D-galactopyranosyl-(1→4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-
(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (20α). [α]25D +61.7 (c = 1, CH2Cl2); 1H-NMR (600 MHz, CDCl3): δ 1.86 (m, 2H,
S13
OCH2CH2CH2N3), 3.15 (dd, 1H, J = 4.8, 8.4 Hz), 3.31-3.38 (m, 6H), 3.43-3.49 (m, 2H), 3.56-3.62 (m, 2H), 3.69-3.71 (m, 2H), 3.82-
3.83 (m, 1H), 3.91-3.98 (m, 2H), 4.06-4.09 (m, 3H), 4.13-4.15 (m, 1H), 4.20 (d, 1H, J = 2.4 Hz), 4.23 (dd, 1H, J = 3.0, 10.2 Hz), 4.28
(s, 2H), 4.34-4.38 (m, 2H), 4.35 (d, 1H, J = 8.4 Hz, H-1’), 4.45-4.48 (m, 2H), 4.46 (d, 1H, J = 7.8 Hz, H-1), 4.52-4.57 (m, 3H), 4.60-
4.62 (m, 1H) 4.66-4.70 (m, 2H), 4.77-4.84 (m, 3H), 4.90-4.92 (m, 1H), 5.10 (d, 1H, J = 11.4 Hz), 5.21 (d, 1H, J = 3.0 Hz, H-1”), 5.55
(dd, 1H, J = 3.0, 10.8 Hz), 6.89-6.91 (m, 1H, aromatic), 6.98-7.01 (m, 2H, aromatic), 7.05-7.07 (m, 2H, aromatic), 7.09-7.38 (m, 40H,
aromatic), 7.72-7.74 (m, 2H, aromatic), 8.11-8.13 (m, 2H, aromatic); 13C-NMR (150 MHz, CDCl3): δ 29.2, 48.3, 66.4, 67.2, 67.3,
68.1, 68.8, 72.3, 72.7, 72.9, 73.0, 73.1 (×2), 73.7, 74.4, 75.0 (×3), 75.1, 75.3, 75.6 (×2), 79.4, 81.4, 81.6, 83.2, 99.8, 102.8, 103.5,
123.2, 126.7, , 127.4 (×2), 127.5 (×3), 127.6 (×3), 127.7 (×2), 127.8 (×2), 127.9, 128.1 (×2), 128.2 (×5), 128.3 (×2), 128.4, 130.6,
135.1, 137.8 (×2), 138.1, 138.2, 138.3, 138.5 (×2), 138.6, 139.4, 150.2, 163.5; gHMQC (without 1H decoupling): 1JC1”,H1” = 170.8 Hz, 1JC1’,H1’ = 161.5 Hz, 1JC1,H1 = 160.7 Hz; ESI-MS [M+Na]+ C91H94N4NaO19 calcd 1569.7, obsd 1570.2.
3-Aminopropyl 2-acetamido-2-deoxy-β-D-galactopyranosyl-(1→3)-α-D-galactopyranosyl-(1→4)-β-D-galactopyranosyl-(1→4)-
β-D-glucopyranoside (23). [α]25D +135 (c = 1, H2O); 1H-NMR (600 MHz, D2O): δ 1.73 (s, 3H), 1.80-1.84 (m, 5H), 2.96 (t, 2H, J =
7.2 Hz), 3.13 (m, 1H), 3.37-3.87 (m, 23H), 4.05 (s, 1H), 4.18 (m, 1H), 4.30 (d, 2H, J = 7.8 Hz), 4.42 (d, 1H, J = 9.0 Hz), 4.70 (d, 1H),
J = 3.6 Hz); 13C-NMR (150 MHz, D2O): δ 22.4, 26.8, 37.6, 52.7, 60.1, 60.4, 60.5, 61.1, 67.7, 67.9 (×2), 69.0, 70.3, 70.9, 71.0 72.2,
73.0, 74.5, 74.9, 75.0, 75.6, 77.3, 78.8, 100.5, 102.1, 103.4 (×2), 175.3, 181.2; 1JC1’’,H1’’ = 171.5 Hz, Other three 1JC1,H1 = 162.9 Hz,
162.9 Hz, 162.9 Hz; HRMS: [M+Na]+ C29H52N2NaO22 calcd 787.2960, obsd 787.2963.
p-Tolyl 2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1→3)-2-azido-4,6-benzylidene-2-deoxy-1-thio-β-D-galactopyranoside
(S1). [α]25D -14.2 (c = 1, CH2Cl2); 1H-NMR (600 MHz, CDCl3): δ 2.25 (s, 3H, SPhCH3), 3.28 (s, 1H, H-5), 3.47-3.58 (m, 5H, H-3, H-
3’,H-5’,H-6a’, H-6b’), 3.79-3.85 (m, 4H, H-2, H-6a, H-2’, H-4’), 4.21 (d, 1H, J3,4 = 3.0 Hz, H-4), 4.26 (d, 1H, JH6a,H6b = 12 Hz, H-6b),
S14
4.38 (d, 1H, J1,2 = 9.6 Hz, H-1), 4.37-4.38 (m, 2H, CH2Ph), 4.56 (d, 1H, J = 12.0 Hz, CH2Ph), 4.65 (d, 1H, J1’,2’ = 7.2 Hz, H-1’), 4.67-
4.76 (m, 3H, CH2Ph), 4.85-4.91 (m, 2H, CH2Ph), 5.43 (s, 1H, CHPh), 6.90-6.95 (m, 2H), 7.13-7.18 (m, 3H), 7.22-7.34 (m, 20H),
7.42-7.44 (m, 2H), 7.59-7.60 (m, 2H). 13C-NMR (150 MHz, CDCl3): δ 21.1, 60.1, 69.0, 69.1, 69.8, 73.0, 73.3, 73.4, 73.5, 74.3, 74.6,
74.8, 78.6 (×2), 82.1, 85.8, 100.3, 104.2, 126.3, 127.2, 127.3, 127.4, 127.5, 127.6, 127.7, 127.8, 127.9, 128.1 (×3), 128.2, 128.3, 128.6,
129.6, 134.0, 137.7, 137.9, 138.1, 138.3, 138.4 (×2); ESI-MS [M+Na]+ C54H55N3NaO9S calcd 944.4, obsd 944.7.
S15
OO
NHTrocSTol
OO
BnOBnO
BnO OBnO
Ph
1H-NMR (600 MHz, CDCl3)
5
11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S16
OO
NHTrocSTol
OO
BnOBnO
BnO OBnO
Ph
13C-NMR (150 MHz, CDCl3)
5
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S17
OO
NHTrocSTol
OO
BnOBnO
BnO OBnO
Ph
gCOSY (600 MHz, CDCl3)
5
8 7 6 5 4 3 2 1 0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
S18
OO
NHTrocSTol
OO
BnOBnO
BnO OBnO
Ph
5
gHMQC (600 MHz, CDCl3)
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S19
OO
NHTrocSTol
OO
BnOBnO
BnO OBnO
Ph
5
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S20
OO
NHTrocSTol
OO
BnOBnO
BnO OBnO
Ph
5
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
162.2 Hz
161.8 Hz
S21
OO
BnO
BnO
OBnO
BnOO
BnOBnO
O
OO
TrocHN
OBn
OBn
O
O N3
O
O
Ph
OBn
OBnO
BnO
BnO OBn
1H-NMR (600 MHz, CDCl3)
4α
12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
S22
OO
BnO
BnO
OBnO
BnOO
BnOBnO
O
OO
TrocHN
OBn
OBn
O
O N3
O
O
Ph
OBn
OBnO
BnO
BnO OBn
4α
13C-NMR (150 MHz, CDCl3)
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S23
gCOSY (600 MHz, CDCl3)4α
8 7 6 5 4 3 2 1 0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
S24
gHMQC (600 MHz, CDCl3)4α
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S25
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
4α
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S26
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
4α
169.0 Hz
162.4 Hz (2)
160.7 Hz (2)
S27
OOTrocHN
OBnO
OBnO
BnO OBn
OBnO
BnO
O OBn
O OBnO
BnOO
OBnN3
OO
Ph
OBnO
BnO
BnO
1H-NMR (600 MHz, CDCl3)
4β
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 0.5 0.0 -0.5 -1.0ppm
S28
OOTrocHN
OBnO
OBnO
BnO OBn
OBnO
BnO
O OBn
O OBnO
BnOO
OBnN3
OO
Ph
OBnO
BnO
BnO
13C-NMR (150 MHz, CDCl3)
4β
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S29
gCOSY (600 MHz, CDCl3) 4β
8 7 6 5 4 3 2 1 0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
S30
gHMQC (600 MHz, CDCl3) 4β
8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S31
gHMQC (without 1H decoupling) (600 MHz, CDCl3) 4β
8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S32
gHMQC (without 1H decoupling) (600 MHz, CDCl3) 4β
161.4 Hz
163.8 Hz
162.8 Hz (2)
159.2 Hz
S33
OO
HO
HO
OHO
HOO
HOHOO
OO
NHAc
OH
OH
HO
O NH2
O OH
OHO
OH
HO OH OH
AcOH3
1H-NMR (600 MHz, D2O)
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 0.0 -0.5ppm
S34
OO
HO
HO
OHO
HOO
HOHOO
OO
NHAc
OH
OH
HO
O NH2
O OH
OHO
OH
HO OH OH
AcOH3
13C-NMR (150 MHz, D2O)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
S35
gCOSY (600 MHz, D2O)3
11 10 9 8 7 6 5 4 3 2 1 0 -1
-1
0
1
2
3
4
5
6
7
8
9
10
11
S36
gHMQC (600 MHz, D2O)3
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S37
gHMQC (600 MHz, D2O)3
4.80 4.75 4.70 4.65 4.60 4.55 4.50 4.45 4.40 4.35 4.30 4.25
98.0
98.5
99.0
99.5
100.0
100.5
101.0
101.5
102.0
102.5
103.0
103.5
104.0
104.5
105.0
105.5
106.0
106.5
S38
gHMQC (without 1H decoupling) (600 MHz, D2O)
3
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S39
gHMQC (without 1H decoupling) (600 MHz, D2O)
3
170.5 Hz
162.0 Hz (2)
158.0 Hz
161.9 Hz
S40
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
OAcO
TrocHN
AcO OAcO
OBnO
BnO OBn
STol
1H-NMR (600 MHz, CDCl3)
11
S41
OAcO
TrocHN
AcO OAcO
OBnO
BnO OBn
STol
11
13C-NMR (150 MHz, CDCl3)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
S42
OAcO
TrocHN
AcO OAcO
OBnO
BnO OBn
STol
11
gCOSY (600 MHz, CDCl3)
7 6 5 4 3 2 1 0 -1
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
S43
OAcO
TrocHN
AcO OAcO
OBnO
BnO OBn
STol
11
gHMQC (600 MHz, CDCl3)
7 6 5 4 3 2 1 0 -1
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S44
OAcO
TrocHN
AcO OAcO
OBnO
BnO OBn
STol
11
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S45
OAcO
TrocHN
AcO OAcO
OBnO
BnO OBn
STol
11
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
1JC1,H1 = 157.9 Hz
1JC1',H1' = 161.8 Hz
S46
OO
TrocHN
OO
BnOBnO
BnO OBnO
Ph
OO
BnO
BnO OBn
STol
1H-NMR (600 MHz, CDCl3)
12
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S47
OO
TrocHN
OO
BnOBnO
BnO OBnO
Ph
OO
BnO
BnO OBn
STol
12
13C-NMR (150 MHz, CDCl3)
250 200 150 100 50 0ppm
S48
OO
TrocHN
OO
BnOBnO
BnO OBnO
Ph
OO
BnO
BnO OBn
STol
12
gCOSY (600 MHz, CDCl3)
7 6 5 4 3 2 1 0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
S49
OO
TrocHN
OO
BnOBnO
BnO OBnO
Ph
OO
BnO
BnO OBn
STol
12
gHMQC (600 MHz, CDCl3)
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S50
OO
TrocHN
OO
BnOBnO
BnO OBnO
Ph
OO
BnO
BnO OBn
STol
12
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S51
OO
TrocHN
OO
BnOBnO
BnO OBnO
Ph
OO
BnO
BnO OBn
STol
12
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
H1
C1
1JH1,C1 = 159.2 Hz
1JH1',C1' = 163.3 Hz
1JH1'',C1'' = 161.1 Hz
H1' H1''
C1'
C1''
S52
OO
BnO
BnO OBnO
BnOO
BnO OBnO
OTrocHN
OO
Ph
O
BnO OBnOBn
STol
1H-NMR (600 MHz, CDCl3)
13
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S53
13C-NMR (150 MHz, CDCl3)
OO
BnO
BnO OBnO
BnOO
BnO OBnO
OTrocHN
OO
Ph
O
BnO OBnOBn
STol
13
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20ppm
S54
gCOSY (600 MHz, CDCl3)13
8 7 6 5 4 3 2 1 0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
S55
gHMQC (600 MHz, CDCl313
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S56
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
13
7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S57
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
13
159.5 Hz
170.2 Hz
159.5 Hz
161.2 Hz
S58
OO
BnO
BnO
OBnO
BnOO
BnOBnO
O
OAcO
TrocHN
OBn
OBn
AcO
O N3
O OBn
OAc
1H-NMR (600 MHz, CDCl3)
17α
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S59
OO
BnO
BnO
OBnO
BnOO
BnOBnO
O
OAcO
TrocHN
OBn
OBn
AcO
O N3
O OBn
OAc
17α
13C-NMR (150 MHz, CDCl3)
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S60
17α
gCOSY (600 MHz, CDCl3)
7 6 5 4 3 2 1
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
S61
17α
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
7 6 5 4 3 2 1
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S62
17α
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
169.5 Hz
163.0 Hz163.0 Hz
160.0 Hz
S63
Op-NO2BzO
BnO
BnO OBn
STol
1H-NMR (600 MHz, CDCl3)
19
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S64
Op-NO2BzO
BnO
BnO OBn
STol
13C-NMR (150 MHz, CDCl3)
19
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S65
Op-NO2BzO
BnO
BnO OBn
STol
gCOSY (600 MHz, CDCl3)
19
9 8 7 6 5 4 3 2 1 0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
S66
O
BnO
OBnO
BnO
OBnO
Op-NO2BzO
BnO
BnO OBn
O N3OBnO
OBn
1H-NMR (600 MHz, CDCl3)
20α
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S67
O
BnO
OBnO
BnO
OBnO
Op-NO2BzO
BnO
BnO OBn
O N3OBnO
OBn
13C-NMR (150 MHz, CDCl3)
20α
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S68
O
BnO
OBnO
BnO
OBnO
Op-NO2BzO
BnO
BnO OBn
O N3OBnO
OBn
gCOSY (600 MHz, CDCl3)
20α
9 8 7 6 5 4 3 2 1 0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
S69
O
BnO
OBnO
BnO
OBnO
Op-NO2BzO
BnO
BnO OBn
O N3OBnO
OBn
gHMQC (600 MHz, CDCl3)
20α
9 8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S70
O
BnO
OBnO
BnO
OBnO
Op-NO2BzO
BnO
BnO OBn
O N3OBnO
OBn
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
20α
9 8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S71
O
BnO
OBnO
BnO
OBnO
Op-NO2BzO
BnO
BnO OBn
O N3OBnO
OBn
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
20α
170.8 Hz
161.7 Hz
161.5 Hz
S72
OO
HO
HO
OHO
HOO
HOHOO
OO
NHAc
OH
OH
HO
O NH2
O OH
OO
OH
OH OH OHO
OH
CO2H
AcHN
OHOHHO
1H-NMR (600 MHz, D2O)
2b
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
S73
OO
HO
HO
OHO
HOO
HOHOO
OO
NHAc
OH
OH
HO
O NH2
O OH
OO
OH
OH OH OHO
OH
CO2H
AcHN
OHOHHO
2b
13C-NMR (150 MHz, D2O)
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10
S74
gCOSY (600 MHz, D2O)2b
6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
S75
gHMQC (600 MHz, D2O)2b
6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S76
gHMQC (600 MHz, D2O)2b
4.8 4.7 4.6 4.5 4.4 4.3 4.2
97
98
99
100
101
102
103
104
105
106
107
108
S77
gHMQC (without 1H decoupling) (600 MHz, D2O)
2b
6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S78
gHMQC (without 1H decoupling) (600 MHz, D2O)
2b
171.0 Hz
160.4 Hz
163.8 Hz (x2)
161.2 Hz
S79
OO
HO
HO
OHO
HOO
HOHOO
OHO
NHAc
OH
OH
HO
O NH2
O OH
OH
1H-NMR (600 MHz, D2O)
23
12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S80
OO
HO
HO
OHO
HOO
HOHOO
OHO
NHAc
OH
OH
HO
O NH2
O OH
OH
23
13C-NMR (150 MHz, D2O)
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S81
gCOSY (600 MHz, D2O)23
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
S82
gHMQC (600 MHz, D2O)23
9 8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
S83
gHMQC (600 MHz, D2O)23
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
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
S84
gHMQC (without 1H decoupling) (600 MHz, D2O)
23
9 8 7 6 5 4 3 2 1 0
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S85
gHMQC (without 1H decoupling) (600 MHz, D2O)
23
171.5 Hz
162.9 Hz (X2)
162.9 Hz
S86
OO
N3
STol
OO
Ph
OBnO
BnO
BnO OBn
1H-NMR (600 MHz, CDCl3)
S1
11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm
S87
OO
N3
STol
OO
BnOBnO
BnO OBnO
Ph
13C-NMR (150 MHz, CDCl3)
S1
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 -30 -40ppm
S88
OO
N3
STol
OO
BnOBnO
BnO OBnO
Ph
gCOSY (600 MHz, CDCl3)
S1
8 7 6 5 4 3 2 1
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
S89
OO
N3
STol
OO
BnOBnO
BnO OBnO
Ph
gHMQC (600 MHz, CDCl3)
S1
8 7 6 5 4 3 2
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S90
OO
N3
STol
OO
BnOBnO
BnO OBnO
Ph
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
S1
8 7 6 5 4 3 2
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
S91
OO
N3
STol
OO
BnOBnO
BnO OBnO
Ph
gHMQC (without 1H decoupling) (600 MHz, CDCl3)
S1
H1H1'
C1
C1'
1JH1,C1 = 162.0 Hz
1JH1,C1 = 159.7 Hz