Supporting Information - Wiley-VCHHigh-resolution mass spectra were recorded on a Micromass electrospray mass spectrometer equipped with an orthogonal electrospray source (Z-spray)

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

[email protected]

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








S4
















S5








1H–13C gHMQC of compound 20α (600 MHz, CDCl3) S69



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


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


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


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


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


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


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


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


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


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


11

S41

OAcO

TrocHN

AcO OAcO

OBnO

BnO OBn

STol

11


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


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


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


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


1JC1,H1 = 157.9 Hz

1JC1',H1' = 161.8 Hz

S46

OO

TrocHN

OO

BnOBnO

BnO OBnO

Ph

OO

BnO

BnO OBn

STol


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


250 200 150 100 50 0ppm

S48

OO

TrocHN

OO

BnOBnO

BnO OBnO

Ph

OO

BnO

BnO OBn

STol

12


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


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


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


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


13

12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm

S53


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


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


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


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


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


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


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


169.5 Hz

163.0 Hz163.0 Hz

160.0 Hz

S63

Op-NO2BzO

BnO

BnO OBn

STol


19

12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm

S64

Op-NO2BzO

BnO

BnO OBn

STol


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


23

171.5 Hz

162.9 Hz (X2)

162.9 Hz

S86

OO

N3

STol

OO

Ph

OBnO

BnO

BnO OBn


S1

11 10 9 8 7 6 5 4 3 2 1 0 -1 -2ppm

S87

OO

N3

STol

OO

BnOBnO

BnO OBnO

Ph


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


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


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


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


S1

H1H1'

C1

C1'

1JH1,C1 = 162.0 Hz

1JH1,C1 = 159.7 Hz

Documents

Supporting Information - Wiley-VCHHigh-resolution mass spectra were recorded on a Micromass electrospray mass spectrometer equipped with an orthogonal electrospray source (Z-spray)