Synthesis of a β-glucan polysaccharide analogue by an iterative copper-catalyzed azide-acetylene coupling reaction

Article abstract of DOI:10.1016/j.tetlet.2012.05.111

A triazole-linked β-glucan analogue was prepared using a copper-catalyzed azide-acetylene coupling reaction. The alkynylsilyl moiety was inactive under the conditions of the copper-catalyzed azide-acetylene coupling reaction and was readily converted into a terminal acetylene group by treatment with tetrabutylammonium fluoride. Using the method, we successfully synthesized a β-glucan analogue containing three laminaripentaose units.

Full text of DOI:10.1016/j.tetlet.2012.05.111

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Supporting Information for the Paper entitled
Synthesis of a !-glucan polysaccharide analogue by an iterative
cupper-catalyzed azide-acetylene coupling reaction.
Hiroshi Tanaka,* Hiroaki Tago, Yohiyuki Adachi, Naohito Ohno, Takashi Takahashi*
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1-H-101
Ookayama, Meguro, Tokyo 152-8552 Japan.
Fax: +81-3-5734-2884
E-mail: thiroshi@apc.titech.ac.jp

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Experimental Section
General Techniques
NMR spectra were recorded on a JEOL Model EX-270 (270 MHz for H, 67.8 MHz for 13C) or a JEOL
1
Model ECP-400 (400 MHz for 1H, 100 MHz for 13C) instrument in the indicated solvent. Chemical shifts are
reported in units parts per million (ppm) relative to the signal (0.00 ppm) for internal tetramethylsilane for
solutions in CDCl3. 1H NMR spectrum data are reported as follows: CDCl3 (7.26 ppm), CD3OD (3.30 ppm),
Acetone-d6 (2.04 ppm) or D2O (HOD (4.7015 ppm at 303 K, 4.5977 ppn at 313 K)). 13C NMR spectrum
data are reported as follows: CDCl3 (77.0 ppm), CD3OD (49.3 ppm) or Acetone-d6 (30.3 ppm) as internal
standard for D2O. Multiplicities are reported by using the following abbreviations: s; singlet, d; doublet, t;
triplet, q; quartet, m; multiplet, br; broad, J; coupling constants in Hertz.
IR spectra was recorded on a Perkin-Elmer Spectrum One FT-IR spectrophotometer. Only the strongest
and/or structurally important peaks are reported as the IR data given in cm-1.
Optical rotations were measured with JASCO model P-1020 polarimeter.
All reactions were monitored by thin-layer chromatography carried out on 0.2 mm E. Merck silica gel
plates (60F-254) with UV light, visualized by 10% ethanolic phosphomolybdic acid, p-anisaldehyde solution
or 0.5% ninhydrin n-butanol solution.
Merck silica gel was used for column chromatography.
Gel permeation chromatography (GPC) for qualitative analysis were performed on Japan Analytical
Industry Model LC908 (recycling preparative HPLC), on a Japan Analytical Industry Model RI-5 refractive
index detector and on a Japan Analytical Industry Model 310 ultra violet detector with a polystyrene gel
column (JAIGEL-1H, 20mm x 600 mm), using chloroform as solvent (3.5 mL/min).
ESI-TOF Mass spectra were measured with Waters LCT PremierTM XE. HRMS (ESI-TOF) were
calibrated with leucine enkephalin.
Dry THF, dry CH2Cl2, dry toluene, dry CH3CN were purified by GlassContour. Dry EtOH was distilled
from Mg(OEt)2.

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1-[2,4,6-Tri-O-benzoyl-3-O-(3-tert-butyldimethylsilyl-prop-2-yn-1-yl)-!-D-glucopyranosyl]-4-phenyl-1H-
1,2,3-triazole(11)
A
mixture
of
2,4,6-tri-O-benzoyl-3-[O-(3-tert-butyldimethylsilyl)prop-2-yn-1-yl]-!-D-glucopyranosyl azide (10) (151 mg,
213 µmol, 1.00 eq.) and phenylacetylene (68.7 µL, 639 µmol, 3.00 eq.) in CH2Cl2 (854 µL) was added Na
ascorbate (427 µL, 0.500 M solution in H2O, 213 µmol, 1.00 eq.) and CuSO4 (427 µL, 0.500 M solution in
H2O, 213 µmol, 1.00 eq.) at room temperature. After being stirred at the same temperature for 2 days, the
reaction mixture was poured into saturated aq. NaHCO3. The aqueous layer was extracted with two portions
of ethyl acetate. The combined extract was washed with saturated aq. NaHCO3 and brine, dried over Na2SO4,
and evaporated in vacuo. The residue was purified by column chromatography on silica gel with 97:3
toluene:acetone to give phenyltriazole 11 (108 mg, 133 µmol, 63%).
Rf = 0.40 (hexane/ethyl acetate = 1/1).
["]D30 = -93.7 (c = 1.00, CHCl3).
1H NMR (400 MHz, CDCl3) # 8.14 (s, 1H, b), 7.32-8.11 (m, 20H, aromatic), 6.16 (d, 1H, H-1, J = 9.3 Hz),
5.81 (dd, 1H, H-2, J = 9.3, 9.3 Hz), 5.69 (dd, 1H, H-4, J = 9.8, 9.8 Hz), 4.63-4.68 (m, 2H, H-3, H-6), 4.45 (dd,
1H, H-6, J = 5.4, 12.7 Hz), 4.32-4.34 (m, 3H, H-5, a), 0.91 (s, 9H, t-Bu), 0.05 (s, 3H, SiCH3), 0.04 (s, 3H,
SiCH3).
13C NMR (100 MHz, CDCl3) # 166.1, 165.0, 164.6, 148.4, 133.7, 133.2, 130.0, 129.9, 129.7, 129.4, 128.9,
128.7, 128.6, 128.5, 128.4, 125.9, 117.9, 100.2, 92.1, 86.3, 77.7, 75.5, 72.3, 70.3, 62.9, 60.2, 25.9, 16.4, -4.9.
FT-IR (neat) 3785, 2956, 2858, 1723, 1602, 1452, 1361, 1316, 1259, 1178, 1096, 1070, 1027, 825, 709 cm-1.
HRMS (ESI-TOF) calcd for C44H46N3O8Si [M+H]+ 772.3054, found 772.3053.
BzO
BzO
a
O
N N
R
N
O
Ph
BzO
b
1-[2,4,6-Tri-O-benzoyl-3-O-(prop-2-yn-1-yl)-!-D-glucopyranosyl]-4-phenyl-1H-1,2,3-triazole (12)
To a stirred solution of the silyl alkyne 11 (131 mg, 162 µmol, 1.00 eq.) in THF (757 µL) was added
TBAF (243 µL, 1.00 M solution in THF, 243 µmol, 1.50 eq.) at 0 °C. After being stirred at the same
temperature for 2 h, the reaction mixture was poured into H2O. The aqueous layer was extracted with two
portions of ethyl acetate. The combined extract was washed with brine, dried over Na2SO4, and evaporated
in vacuo. The residue was purified by column chromatography on silica gel with 95:5 toluene:ethyl acetate
to give terminal acetylene 12 (103 mg, 149 µmol, 92%).
Rf = 0.33 (toluene/ethyl acetate = 9/1).

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["]D30 = -139 (c = 0.310, CHCl3).
1H NMR (400 MHz, CDCl3) # 8.12 (s, 1H, b), 7.32-8.11 (m, 20H, aromatic), 6.18 (d, 1H, H-1, J = 9.3 Hz),
5.81 (dd, 1H, H-2, J = 9.3, 9.3 Hz), 5.69 (dd, 1H, H-4, J = 9.3, 9.3 Hz), 4.45 (dd, 1H, H-6, J = 2.4, 9.8 Hz),
4.43-4.49 (m, 2H, H-3, H-6), 4.33-4.38 (m, 1H, H-5), 4.25 (d, 2H, a, J = 2.4 Hz), 2.12 (t, 1H, CCH, J = 2.4
Hz).
13C NMR (100 MHz, CDCl3) # 165.0, 164.6, 148.4, 133.7, 133.2, 130.0, 129.9, 129.8, 129.4, 128.8, 128.6,
128.4, 125.9, 117.8, 86.2, 79.0, 78.7, 75.7, 75.5, 72.2, 70.2, 62.9, 59.8.
FT-IR (neat) 3286, 3066, 1720, 1602, 1584, 1484, 1451, 1412, 1358, 1316, 1263, 1178, 1097, 1071, 1027,
976, 914, 839, 765, 709 cm-1.
HRMS (ESI-TOF) calcd for C38H32N3O8 [M+H]+ 658.2189, found 658.2181.
BzO
BzO
a
O
N N
N
O
Ph
BzO
b
2,4,6-Tri-O-benzoyl-3-O-{1-[2,4,6-tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!-D-gluco
pyranosyl]-1H-1,2,3-triazol-4-yl}methyl-!-D-glucopyranosyl 4-phenyl-1H-[1,2,3]triazole (13)
A mixture of terminal acetylene 12 (6.20 mg, 8.92 µmol, 1.00 eq.) and glycosyl azide 10 (7.60 mg,
10.7 µmol, 1.20 eq.) in H2O (0.946 mL) and CH2Cl2 (1.00 mL) was added Na ascorbate (36.0 µL, 0.500 M
solution in H2O, 18.0 µmol, 2.00 eq.) and CuSO4 (18.0 µL, 0.500 M solution in H2O, 9.00 µmol, 1.00 eq.) at
room temperature. After being stirred at the same temperature for 1 d, the reaction mixture was poured into
saturated aq. NaHCO3. The aqueous layer was extracted with two portions of ethyl acetate. The combined
extract was washed with brine, dried over Na2SO4, and evaporated in vacuo. The residue was purified by
column chromatography on silica gel with 70:30 toluene:ethyl acetate to give ditriazole (13) (10.7 mg, 7.63
µmol, 86%).
Rf = 0.42 (toluene/ethyl acetate = 4/1).
["]D29 = -67.9 (c = 0.780, CHCl3).
1H NMR (400 MHz, CDCl3) # 7.32-8.14 (m, 37H, aromatic), 6.22 (d, 1H, H-A1 or H-B1, J = 9.8 Hz), 5.89
(dd, 1H, H-A2 or H-B2, J = 9.2, 9.2 Hz), 5.82 (d, 1H, H-A1 or H-B1, J = 9.3 Hz), 5.72 (dd, 1H, H-A4 or
H-B4, J = 9.7, 9.7 Hz), 5.51 (dd, 1H, H-A4 or H-B4, J = 9.7, 9.7 Hz), 5.35 (dd, 1H, H-A2 or H-B2, J = 9.7,
9.7 Hz), 4.14-4.64 (m, 12H, H-A3, H-B3, H-A5, H-B5, H-A6, H-B6, a, b), 0.91 (s, 9H, t-Bu), 0.04 (s, 6H,
SiCH3).
13C NMR (100 MHz, CDCl3) # 166.0, 165.1, 164.9, 148.3, 144.7, 134.0, 133.6, 133.2, 130.0, 129.9, 129.7,
129.4, 129.2, 128.7, 128.6, 128.5, 128.3, 125.9, 121.1, 117.8, 100.2, 86.1, 79.1, 77.2, 75.4, 72.8, 72.4, 70.3,
65.6, 63.0, 62.8, 60.1, 29.6, 25.9, 16.4, -4.9.

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FT-IR (neat) 2955, 1730, 1602, 1452, 1361, 1316, 1262, 1178, 1095, 1070, 1027, 826, 709 cm-1.
HRMS (ESI-TOF) calcd for C74H71N6O16Si [M+H]+ 1327.4696, found 1327.4690.
BzO
BzO
BzO
a
BzO
b
O
O
B
N N
A
TBS
N N
N
O
O
N
Ph
OBz
c'
OBz
c
1,2,5,6-Bis-O-isopropylidene-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-"-D-glucofuranose (15)
To a stirred solution of 1,2,5,6-bis-O-isopropylidene-3-O-(prop-2-yn-1-yl)-"-D-glucofuranose (14)
(7.70 g, 25.8 mmol, 1.00 eq.) in THF (62.5 mL) was added dropwise n-BuLi (16.4 mL, 1.65 M solution in
hexane, 27.1 mmol, 1.05 eq.) at -78 °C. After being stirred at the same temperature for 5 min, TBSCl (4.28
g, 28.4 mmol, 1.10 eq.) in THF (15.0 mL) was added dropwise. After being stirred at 0 °C for 1 h, the
reaction mixture was poured into saturated aq. NH4Cl. The aqueous layer was extracted with two portions of
ethyl acetate. The combined extract was washed with saturated aq. NH4Cl and brine, dried over MgSO4, and
evaporated in vacuo. The residue was purified by column chromatography on silica gel with 97:3
hexane:ethyl acetate to give alkynylsilane 15 (9.46 g, 22.9 mmol, 89%).
Rf = 0.46 (hexane/ethyl acetate = 4/1).
["]D22 = -5.76 (c = 1.15, CHCl3).
1H NMR (400 MHz, CDCl3) # 5.84 (d, 1H, H-1, J = 3.9 Hz), 4.67 (d, 1H, H-2, J = 3.9 Hz), 4.19-4.29 (m, 3H,
H-6, a), 4.12 (dd, 1H, H-5, J = 2.9, 7.8 Hz), 4.03-4.07 (m, 2H, H-3, H-6), 3.97 (dd, 1H, H-4, J = 5.4, 8.8 Hz),
1.47 (s, 3H, Me), 1.39 (s, 3H, Me), 1.31 (s, 3H, Me), 1.27 (s, 3H, Me), 0.92 (s, 9H, t-Bu), 0.10 (s, 6H, SiCH3).
13C NMR (100 MHz, CDCl3) # 111.7, 108.9, 105.2, 101.8, 90.2, 82.7, 81.6, 81.0, 72.6, 67.0, 58.8, 26.8, 26.2,
26.0, 25.3, 16.4, -4.8.
FT-IR (neat) 2988, 2934, 2859, 1463, 1372, 1252, 1209, 1166, 1080, 1029, 841, 826, 812, 683 cm-1.
HRMS (ESI-TOF) calcd for C21H37O6Si [M+H]+ 413.2359, found 413.2351.
O
O
O
O
H
O
O
a
TBS
1,2,4,6-Tetra-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-"/!-D-glucopyranose (16)
To a stirred solution of diacetal 15 (3.41 g, 8.26 mmol, 1.00 eq.) in THF (50.0 mL) and H2O (20.0
mL) was added trifluoroacetic acid (50.0 mL) at room temperature. After being stirred at 60 °C for 5 h, the

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reaction mixture was evaporated in vacuo. The residue was poured into saturated aq. NaHCO3. The
aqueous layer was extracted with three portions of ethyl acetate. The combined extract was washed with
saturated aq. NaHCO3 and brine, dried over MgSO4, and evaporated in vacuo. The residue was used for the
next reaction without further purification.
To a stirred solution of the residue in pyridine (30.0 mL) was added benzoyl chloride (5.52 mL, 47.9
mmol, 5.80 eq.) and a catalytic amount of DMAP at room temperature. After being stirred at the same
temperature for 13 h, the reaction mixture was quenched with MeOH and 1 M HCl. The aqueous layer was
extracted with two portions of ethyl acetate. The combined extract was washed with 1 M HCl and saturated
aq. NaHCO3 and brine, dried over Na2SO4, and evaporated in vacuo. The residue was purified by column
chromatography on silica gel with 95:5 hexane:ethyl acetate to give the benzoyl glycoside 16 (5.19 g, 6.94
mmol, 2 steps 84%, ":! = 56:44).
Rf = 0.39, 0.44 (hexane/ethyl acetate = 2/1).
["]D24 = -6.51 (c = 1.07, CHCl3).
1H NMR (270 MHz, CDCl3) # 7.99-8.11 (m, 8H, aromatic), 7.38-7.54 (m, 12H, aromatic), 6.78 (d, 0.56H,
H-1", J = 4.0 Hz), 6.15 (d, 0.44H, H-1!, J = 7.6 Hz), 5.60-5.70 (m, 1.44H, H-2!, H-4", H-4!), 5.48 (dd,
0.56H, H-2", J = 4.6, 10.5 Hz), 4.79 (t, 0.56H, H-3", J = 8.1 Hz), 4.22-4.65 (m, 5.44H, H-3!, H-5", H-5!,
H-6", H-6!, a", a!), 0.88 (s, 9H, t-Bu), 0.03 (s, 6H, SiCH3).
13C NMR (100 MHz, CDCl3) # 166.1, 165.2, 165.1, 165.0, 164.8, 164.3, 133.7, 133.5, 133.4, 133.0, 130.2,
129.9, 129.8, 129.7, 129.6, 129.3, 129.2, 128.6, 128.5, 128.3, 100.9, 100.6, 92.6, 91.1, 90.1, 77.2, 74.6, 73.1,
72.4, 72.0, 70.3, 62.9, 62.7, 60.0, 59.8, 25.9, 16.4, 16.3, -4.8, -4.9.
FT-IR (neat) 3065, 2954, 2929, 2858, 1734, 1602, 1452, 1362, 1316, 1266, 1178, 1094, 1069, 1027, 840, 826,
754, 709, 686, 581 cm-1.
HRMS (ESI-TOF) calcd for C43H45O10Si [M+H]+ 749.2782, found 749.2772.
BzO
BzO
O
TBS
O
OBz
OBz
2,4,6-Tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-D-glucopyranose (17)
A mixture of benzoyl glycoside (8.00 g, 10.7 mmol, 1.00 eq.) and acetic acid (1.20 mL) in DMF
(42.8 mL) was added hydrazine monohydrate (1.00 mL) at 0 °C. After being stirred at the same temperature
for 4 h, the reaction mixture was poured into 1 M HCl. The aqueous layer was extracted with three portions
of ethyl acetate. The combined extract was washed with 1 M HCl and H2O and saturated aq. NaHCO3 and
brine, dried over Na2SO4, and evaporated in vacuo. The residue was purified by column chromatography on
silica gel with 97:3 toluene:ethyl acetate to give hemicatal 17 (6.10 g, 9.48 mmol, 89%).

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Rf = 0.34 (hexane/ethyl acetate = 2/1).
["]D31 = +45.8 (c = 0.640, CHCl3).
1H NMR (270 MHz, CDCl3) " anomer (major); # 8.02-8.13 (m, 6H, aromatic), 7.36-7.58 (m, 9H, aromatic),
5.65 (d, 1H, H-1, J = 3.3 Hz), 5.52 (dd, 1H, H-4 or H-6, J = 9.6, 9.6 Hz), 5.12 (dd, 1H, H-2, J = 4.1, 9.9 Hz),
4.69 (dd, 1H, H-4 or H-6, J = 9.6, 9.6 Hz), 4.61 (dd, 1H, H-6, J = 2.6, 12.2 Hz), 4.33-4.54 (m, 4H, H-3, H-5,
a), 0.88 (s, 9H, t-Bu), 0.03 (s, 6H, SiCH3).
13C NMR (100 MHz, CDCl3) # 166.4, 165.7, 165.2, 133.3, 133.0, 129.8, 129.7, 129.6, 129.5, 129.0, 128.4,
128.2, 125.2, 101.2, 90.8, 90.2, 77.2, 75.0, 74.1, 70.7, 67.6, 62.9, 60.4, 25.9, 16.3, -4.9.
FT-IR (neat) 3684, 2955, 2858, 1728, 1602, 1452, 1316, 1270, 1178, 1110, 1070, 1027, 826, 777, 710, 686
cm-1.
HRMS (ESI-TOF) calcd for C36H41O9Si [M+H]+ 645.2520, found 645.2523.
BzO
BzO
O
TBS
O
OH
OBz
O-[2,4,6-Tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-",!-D-glucopyranosyl]
trichloroacetimidate (6)
A mixture of hemiacetal 17 (6.10 g, 9.48 mmol, 1.00 eq.) and a catalytic amount of Cs2CO3 in
CH2Cl2 (37.9 mL) was added Cl3CCN (5.90 mL, 56.9 mmol, 6.00 eq.) at 0 °C. After being stirred at room
temperature for 2 h, the reaction mixture was filtered through a pad of Celite. The filtrate mixture was
evaporated in vacuo. The residue was purified by column chromatography on silica gel with 99:1
toluene:ethyl acetate to give glycosyl imidate 6 (7.18 g, 9.10 mmol, 96%).
Rf = 0.49 (hexane/ethyl acetate = 2/1).
["]D22 = +59.0 (c = 1.03, CHCl3).
1H NMR (400 MHz, CDCl3) " anomer (major); # 8.60 (s, 1H, NH), 8.00-8.10 (m, 6H, aromatic), 7.52-7.59 (m,
3H, aromatic), 7.38-7.47 (m, 6H, aromatic), 6.73 (d, 1H, H-1, J = 3.9 Hz), 5.60 (dd, 1H, H-4, J = 10.2, 10.2
Hz), 5.42 (dd, 1H, H-2, J = 3.9, 9.8 Hz), 4.75 (dd, 1H, H-3, J = 9.3, 9.3 Hz), 4.59 (dd, 1H, H-6, J = 2.4, 12.4
Hz), 4.46-4.51 (m, 1H, H-5), 4.33-4.43 (m, 3H, H-6, a), 0.90 (s, 9H, t-Bu), 0.05 (s, 3H, SiCH3), 0.05 (s, 3H,
SiCH3).
13C NMR (100 MHz, CDCl3) # 166.0, 165.1, 160.3, 137.7, 133.4, 132.9, 129.9, 129.8, 129.7, 129.2, 129.0,
128.9, 128.4, 128.2, 128.1, 125.2, 100.8, 93.1, 91.0, 90.8, 74.5, 72.6, 70.4, 69.9, 62.6, 60.0, 25.9, 21.3, 16.3,
-4.8.
FT-IR (neat) 3344, 2954, 2858, 1732, 1677, 1602, 1452, 1268, 1108, 1028, 908, 839, 796, 710, 647 cm-1.
HRMS (ESI-TOF) calcd for C38H41Cl3NO9Si [M+H]+ 788.1616, found 788.1614.

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BzO
BzO
O
TBS
O
O
NH
CCl3
OBz
Ethylthio 2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-ꢀ
O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranos
ide (20)
A mixture of diol 18 (1.86 g, 2.79 mmol, 1.10 eq.), the glycoyl imidate 6 (2.00 g, 2.54 mmol, 1.00
eq.) and pulverized activated MS-4A (7.60 g) in dry CH2Cl2 (508 mL) was stirred at room temperature for 1 h
under argon to remove a trace amount of water. Then the reaction mixture was cooled to -78 °C. To the
mixture was added a catalytic amount of TMSOTf. After being stirred at the same temperature for 2 h, the
reaction mixture was neutralized with triethylamine and filtered through a pad of Celite. The filtrate mixture
was evaporated in vacuo. The residue was used for the next reaction without further purification.
To a stirred solution of the residue in pyridine (10.5 mL) was added acetic anhydride (2.00 mL, 21.0
mmol, 8.27 eq.) and a catalytic amount of DMAP at room temperature. After being stirred at the same
temperature for 7 h, the reaction mixture was poured into 1 M HCl. The aqueous layer was extracted with
two portions of ethyl acetate. The combined extract was washed with 1 M HCl, saturated aq. NaHCO3 and
brine, dried over Na2SO4, and evaporated in vacuo. The residue was purified by column chromatography on
silica gel with 95:5 toluene:ethyl acetate to give ethylthio glycoside 20 (1.44 g, 1.08 mmol, 2 steps 43%).
Rf = 0.41 (toluene/ethyl acetate = 9/1).
["]D25 = -14.3 (c = 0.935, CHCl3).
1H NMR (400 MHz, CDCl3) # 8.12 (d, 2H, aromatic, J = 7.3 Hz), 7.94-8.03 (m, 6H, aromatic), 7.11-7.65 (m,
22H, aromatic), 5.52 (s, 1H, benzylidene), 5.49 (dd, 1H, H-C4, J = 9.8, 9.8 Hz), 5.34 (dd, 1H, H-C2, J = 7.8,
7.8 Hz), 4.98 (d, 1H, H-C1, J = 7.8 Hz), 4.83-4.85 (m, 2H, H-A2, H-B2), 4.72 (s, 1H, benzylidene), 4.68 (d,
1H, H-A1, J = 5.4 Hz), 4.47-4.49 (m, 2H, H-B1, H-C6), 4.31-4.36 (m, 2H, H-C3, H-A6), 4.23-4.27 (m, 3H,
H-C6, a), 4.08-4.14 (m, 2H, H-A3, H-B6), 4.00 (dd, 1H, H-B4, J = 8.8, 10.3 Hz), 3.76-3.86 (m, 2H, H-B3,
H-C5), 3.67 (dd, 1H, H-A6, J = 10.4, 10.4 Hz), 3.37-3.54 (m, 3H, H-A5, H-B5, H-B6), 3.23 (dd, 1H, H-A4, J
= 10.0, 10.0 Hz), 2.60-2.68 (m, 2H, SCH2CH3), 1.63 (s, 3H, COCH3), 1.19 (t, 3H, SCH2CH3, J = 7.3 Hz), 0.86
(s, 9H, t-Bu), -0.01 (s, 6H, SiCH3).
13C NMR (100 MHz, CDCl3) # 207.8, 169.1, 166.1, 164.9, 137.2, 133.5, 133.3, 132.9, 129.9, 129.7, 129.4,
129.2, 129.0, 128.7, 128.5, 128.4, 128.2, 127.9, 126.3, 125.9, 101.6, 100.5, 98.5, 98.4, 84.3, 78.4, 77.9, 77.8,
75.8, 73.2, 72.9, 72.0, 71.1, 68.5, 65.4, 63.2, 59.5, 25.9, 24.3, 20.3, 16.4, 14.7, -4.9.
FT-IR (neat) 3675, 2929, 2859, 1732, 1603, 1452, 1374, 1316, 1266, 1178, 1096, 1070, 1027, 839, 749, 710
cm-1.

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
BzO
BzO
O
Ph
O
O
Ph
O
O
O
O
O
O
a
B
A
TBS
O
SEt
OBz
OAc
OBz
2-O-Benzoyl-4,6-O-benzylidene-3-O-(4,6-O-benzylidene-2,3-di-O-levulinoyl-!-D-glucopyranosyl)-!-D-glu
copyranosyl azide (21)
A
mixture of ethylthio 2-O-benzoyl-4,6-O-benzylidene-3-O-(4,6-O-benzylidene-2,3-di-O-ꢀ
levulinoyl-!-D-glucopyranosyl)-!-D-glucopyranoside (7) (4.00 g, 4.64 mmol, 1.00 eq.) and pulverized
activated MS-4A (9.30 g, 2.00 g/mmol) in dry CH2Cl2 (46.2 mL, 10.0 mL/mmol) was stirred at room
temperature for 1 h under argon to remove a trace amount of water. Then the reaction mixture was cooled to
-78 °C. To the mixture was added IBr (5.56 mL, 1.00 M solution in CH2Cl2, 5.56 mmol, 1.20 eq.). After
being stirred at 0 °C for 30 min, the reaction mixture was neutralized with triethylamine and filtered through a
pad of Celite. The filtrate mixture was poured into 10% aq. Na2S2O3 and saturated aq. NaHCO3. The
aqueous layer was extracted with three portions of ethyl acetate. The combined extract was washed with
10% aq. Na2S2O3 and saturated aq. NaHCO3 and brine, dried over Na2SO4, and evaporated in vacuo. The
residue was used for the next reaction without further purification.
To a stirred solution of the residue in DMF (23.1 mL) was added sodium azido (756 mg, 11.6 mmol,
2.50 eq.) at room temperature. After being stirred at the same temperature for 3 h, the reaction mixture was
poured into saturated aq. NaHCO3. The aqueous layer was extracted with two portions of ethyl acetate.
The combined extract was washed with 1 M HCl and H2O and saturated aq. NaHCO3 and brine, dried over
Na2SO4 , and evaporated in vacuo. The residue was purified by column chromatography on silica gel with
95:5
toluene:acetone
to
give
2-O-Benzoyl-4,6-O-benzylidene-3-O-(4,6-O-benzylidene-2,3-di-O-levulinoyl-!-D-glucopyranosyl)-!-D-gluco
pyranosyl azide (21) (3.21 g, 3.81 mmol, 2 steps 82%).
Rf = 0.46 (toluene/ethyl acetate = 2/1).
["]D25 = -68.3 (c = 0.835, CHCl3).
1H NMR (400 MHz, CDCl3) # 8.05 (d, 2H, aromatic, J = 7.8 Hz), 7.16-7.65 (m, 13H, aromatic), 5.59 (s, 1H,
benzylidene), 5.38 (s, 1H, benzylidene), 5.25 (dd, 1H, H-A2, J = 9.3, 9.3 Hz), 5.10 (dd, 1H, H-B3, J = 9.8, 9.8
Hz), 5.01 (dd, 1H, H-B2, J = 7.8, 7.8 Hz), 4.71 (d, 1H, H-B1, J = 8.8 Hz), 4.69 (d, 1H, H-A1, J = 8.8 Hz),
4.42 (dd, 1H, H-A6, J = 4.4, 10.2 Hz), 4.25 (dd, 1H, H-B6, J = 4.9, 10.8 Hz), 4.19 (dd, 1H, H-A3, J = 9.3, 9.3
Hz), 3.77-3.88 (m, 2H, H-A4, H-A6), 3.61-3.68 (m, 3H, H-B4, H-A5, H-B6), 3.36-3.42 (m, 1H, H-B5),
2.31-2.68 (m, 8H, a, b, c, d), 2.08 (s, 6H, COCH3).
13C NMR (100 MHz, CDCl3) # 206.2, 171.6, 171.2, 164.8, 136.9, 136.6, 133.7, 129.7, 129.1, 128.8, 128.7,

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
128.1, 128.0, 126.0, 125.9, 101.1, 101.0, 100.8, 88.4, 78.2, 78.1, 77.2, 72.8, 71.5, 71.4, 68.7, 68.3, 68.0, 66.1,
37.6, 37.5, 29.5, 27.7, 27.2.
FT-IR (neat) 2872, 2119, 1721, 1371, 1268, 1152, 1099, 1028, 700 cm-1.
HRMS (ESI-TOF) calcd for C43H46N3O15 [M+H]+ 844.2929, found 844.2917.
O
Ph
O
Ph
O
O
O
O
O
O
O
N3
O
OBz
O
O
O
2-O-Benzoyl-4,6-O-benzylidene-3-O-(4,6-O-benzylidene-!-D-glucopyranosyl)-!-D-glucopyranosyl azide
(22)
A mixture of dilevulinoyl ester 21 (3.11 g, 3.69 mmol, 1.00 eq.) and acetic acid (3.00 mL) in CH2Cl2
(18.4 mL) was added hydrazine monohydrate (1.00 mL) at 0 °C. After being stirred at the same temperature
for 4 h, the reaction mixture was poured into 1 M HCl. The aqueous layer was extracted with two portions of
ethyl acetate. The combined extract was washed with 1 M HCl and H2O and saturated aq. NaHCO3 and brine,
dried over Na2SO4, and evaporated in vacuo. The residue was purified by column chromatography on silica
gel with 92:8 toluene:acetone to give diol 22 (2.14 g, 3.31 mmol, 90%).
Rf = 0.36 (toluene/acetone = 4/1).
["]D25 = -56.3 (c = 1.15, CHCl3).
1H NMR (400 MHz, CDCl3) # 8.06 (d, 2H, aromatic, J = 7.3 Hz), 7.18-7.61 (m, 13H, aromatic), 5.62 (s, 1H,
benzylidene), 5.42 (s, 1H, benzylidene), 5.26 (dd, 1H, H-A2, J = 8.8, 8.8 Hz), 4.87 (d, 1H, H-A1, J = 8.8 Hz),
4.43-4.48 (m, 2H, H-B1, H-A6), 4.21 (dd, 1H, H-A3, J = 9.3, 9.3 Hz), 3.80-3.90 (m, 3H, H-A4, H-A6, H-B6),
3.58-3.68 (m, 2H, H-B3, H-A5), 3.43-3.48 (m, 3H, H-B2, H-B4, H-B6), 3.26-3.32 (m, 1H, H-B5), 2.86 (d, 1H,
OH, J = 2.9 Hz), 2.08 (brs, 1H, OH).
13C NMR (100 MHz, CDCl3) # 165.5, 136.8, 136.4, 133.7, 129.9, 129.5, 129.2, 128.6, 128.3, 126.2, 126.0,
102.9, 101.8, 88.7, 80.1, 78.7, 77.9, 73.3, 72.7, 68.7, 68.3, 66.6.
FT-IR (neat) 3477, 2875, 2119, 1727, 1603, 1452, 1384, 1317, 1270, 1181, 1098, 1029, 1008, 918, 752, 711,
700, 547 cm-1.
O
Ph
O
Ph
O
O
O
O
O
HO
N3
OH
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2-O-Benzoyl-4,6-O-benzylidene-3-O-[4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-
acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!-D-glu
copyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-D-glucopyranosyl azide
(23)
A mixture of ethyl glycoside 20 (976 mg, 0.731 mmol, 1.00 eq.), diol 22 (520 mg, 0.804 mmol, 1.10
eq.) and pulverized activated MS-4A (2.19 g) in dry CH2Cl2 (73.1 mL) was stirred at room temperature for 1 h
under argon to remove a trace amount of water. Then the reaction mixture was cooled to 0 °C. To the
mixture was added MeOTf (827 µL, 7.31 mmol, 10.0 eq.). After being stirred at room temperature for 1 day,
the reaction mixture was neutralized with triethylamine and filtered through a pad of Celite. The filtrate
mixture was evaporated in vacuo. The residue was chromatographed on silica gel with 94:6 toluene:ethyl
acetate to give pentasaccharide 23 (1.15 g, 0.598 mmol, 82%).
Rf = 0.39 (toluene/ethyl acetate = 5/1).
["]D32 = -15.3 (c = 0.130, CHCl3).
1H NMR (400 MHz, CDCl3) # 8.01-8.11 (m, 10H, aromatic), 7.16-7.99 (m, 35H, aromatic), 5.58 (s, 1H,
benzylidene), 5.47-5.52 (m, 2H, H-E4, benzylidene), 5.33 (t, 1H, H-E2, J = 7.8 Hz), 5.19 (dd, 1H, H-A2, J =
8.8, 8.8 Hz), 3.25-5.01 (m, 36H, H-A1, H-B1, H-C1, H-D1, H-E1, H-B2, H-C2, H-D2, H-A3, H-B3, H-C3,
H-D3, H-E3, H-A4, H-B4, H-C4, H-D4, H-A5, H-B5, H-C5, H-D5, H-E5, H-A6, H-B6, H-C6, H-D6, H-E6, a,
benzylidene), 2.70 (brs, 1H, OH) 1.71 (s, 3H, COCH3), 0.86 (s, 9H, t-Bu), -0.01 (s, 6H, SiCH3).
FT-IR (neat) 3851, 3568, 3446, 2927, 2376, 2345, 2118, 1731, 1633, 1384, 1266, 1096, 1028, 756, 712 cm-1.
HRMS (ESI-TOF) calcd for C104H106N3O31Si [M+H]+ 1920.6580, found 1920.6592.
BzO
O
Ph
O
O
O
Ph
O
Ph
O
O
Ph
O
BzO
O
O
O
O
O
O
O
O
O
a
E
D
C
A
B
TBS
O
N3
OBz
OBz
OH
OBz
OBz
2-O-Benzoyl-4,6-O-benzylidene-3-O-(2-O-acetyl-4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylidene
-3-O-(2-O-acetyl-4,6-O-benzylidene-3-O-(2,4,6-tri-O-benzoyl-3-O-(prop-3-tert-butyldimethylsilyl-2-yn-1-
yl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyran
osyl azide (4)
To a stirred solution of pentasaccahride 23 (1.15 g, 0.598 mmol, 1.00 eq.) in pyridine (3.00 mL) was
added acetic anhydride (565 µL, 5.98 mmol, 10.0 eq.) and a catalytic amount of DMAP at room temperature.
After being stirred at the same temperature for 2 h, the reaction mixture was poured into 1 M HCl. The
aqueous layer was extracted with two portions of ethyl acetate. The combined extract was washed with 1 M
HCl and saturated aq. NaHCO3 and brine, dried over MgSO4, and evaporated in vacuo. The residue was
purified by column chromatography on silica gel with 92:8 toluene:ethyl acetate to give acetate 4 (971 mg,

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
0.495 mmol, 83%).
Rf = 0.60 (toluene/ethyl acetate = 4/1).
["]D31 = -21.5 (c = 0.990, CHCl3).
1H NMR (400 MHz, CDCl3) # 7.96-8.15 (m, 10H, aromatic), 7.16-7.67 (m, 35H, aromatic), 5.56 (s, 1H,
benzylidene), 5.51 (dd, 1H, H-E4, J = 9.6, 9.6 Hz), 5.38 (dd, 1H, H-E2, J = 8.8, 8.8 Hz), 5.18 (s, 1H,
benzylidene), 5.33 (d, 1H, H-E1, J = 7.8 Hz), 3.17-4.91 (m, 36H, H-A1, H-B1, H-C1, H-D1, H-A2, H-B2,
H-C2, H-D2, H-A3, H-B3, H-C3, H-D3, H-E3, H-A4, H-B4, H-C4, H-D4, H-A5, H-B5, H-C5, H-D5, H-E5,
H-A6, H-B6, H-C6, H-D6, H-E6, a, benzylidene), 1.77 (s, 3H, COCH3), 1.65 (s, 3H, COCH3), 0.89 (s, 9H,
t-Bu), 0.02 (s, 6H, SiCH3).
13C NMR (100 MHz, CDCl3) # 166.0, 165.0, 164.7, 137.1, 136.9, 133.8, 133.6, 132.8, 129.8, 129.7, 129.4,
129.1, 129.0, 128.9, 128.7, 128.6, 128.4, 128.3, 128.2, 128.1, 128.0, 127.8, 126.3, 126.1, 125.9, 125.2, 101.8,
101.0, 100.8, 98.5, 98.4, 90.9, 88.2, 78.0, 71.9, 71.8, 71.1, 68.8, 65.4, 65.3, 59.5, 25.9, 21.4, 20.4, 20.3, 16.4,
-5.0.
FT-IR (neat) 2930, 2861, 2119, 1733, 1603, 1452, 1375, 1316, 1266, 1179, 1097, 1028, 915, 840, 753, 712
cm-1.
HRMS (ESI-TOF) calcd for C106H108N3O32Si [M+H]+ 1962.6685, found 1962.6730.
BzO
O
Ph
O
O
O
Ph
O
Ph
O
O
Ph
O
BzO
O
O
O
O
O
O
O
O
O
a
E
D
C
A
B
TBS
O
N3
OBz
OBz
OAc
OBz
OBz
1-{2-O-Benzoyl-4,6-O-benzylidene-3-O-[2-O-acetyl-4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylide
ne-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-
1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-D-glucopyr
anosyl}-4-N-(tert-butoxycarbonyl)aminomethyl-1H-1,2,3-triazole (24)
To
a
solution of glycosyl azide
4
(264 mg, 0.134 mmol, 1.00 eq.) and
N-(tert-butoxycarbonyl)-prop-2-ynylamine (62.4 mg, 0.402 mmol, 3.00 eq.) in H2O (2.00 mL) and CH2Cl2
(2.00 mL) was added Na ascorbate (0.538 mL, 0.500 M solution in H2O, 0.269 mmol, 2.00 eq.) and CuSO4
(0.269 mL, 0.500 M solution in H2O, 0.134 mmol, 1.00 eq.) at room temperature. After being stirred at the
same temperature for 2 d, the reaction mixture was poured into saturated aq. NaHCO3. The aqueous layer
was extracted with two portions of ethyl acetate. The combined extract was washed with 1 M HCl, saturated
aq. NaHCO3 and brine, dried over MgSO4, and evaporated in vacuo. The residue was purified by column
chromatography on silica gel with 89:11 toluene:acetone to give triazole 24 (284 mg, 0.134 mmol, quant.).
Rf = 0.42 (toluene/acetone = 5/1).
["]D32 = -24.3 (c = 0.830, CHCl3).
1H NMR (400 MHz, CDCl3) # 7.14-8.09 (m, 46H, aromatic), 5.84 (d, 1H, H-A1, J = 9.3 Hz), 3.19-5.62 (m,

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
42H, H-B1, H-C1, H-D1, H-E1, H-A2, H-B2, H-C2, H-D2, H-E2, H-A3, H-B3, H-C3, H-D3, H-E3, H-A4,
H-B4, H-C4, H-D4, H-E4, H-A5, H-B5, H-C5, H-D5, H-E5, H-A6, H-B6, H-C6, H-D6, H-E6, a, b,
benzylidene), 1.71 (s, 3H, COCH3), 1.61 (s, 3H, COCH3), 1.47 (s, 9H, Boc), 0.86 (s, 9H, t-Bu), -0.02 (s, 6H,
SiCH3).
13C NMR (100 MHz, CDCl3) # 169.0, 168.9, 166.0, 165.0, 164.9, 164.6, 137.1, 136.8, 133.7, 133.3, 132.8,
129.8, 129.7, 129.4, 129.0, 128.7, 128.5, 128.4, 128.3, 128.2, 128.0, 127.8, 126.3, 126.2, 126.1, 125.9, 125.2,
101.9, 101.4, 101.0, 100.5, 98.5, 98.2, 91.0, 78.0, 77.9, 77.8, 74.2, 73.1, 71.9, 71.8, 71.0, 69.9, 68.6, 68.4, 68.0,
65.9, 65.3, 63.1, 59.5, 28.4, 25.9, 21.4, 20.4, 20.2, 16.4, -5.0.
FT-IR (neat) 2930, 1733, 1603, 1500, 1452, 1373, 1316, 1265, 1178, 1097, 1070, 914, 840, 712 cm-1.
HRMS (ESI-TOF) calcd for C114H121N4O34Si [M+H]+ 2117.7632, found 2117.7661.
Ph
O
Ph
Ph
BzO
BzO
Ph
O
O
O
O
O
O
O
O
O
O
O
O
O
O
a
O
O
E
D
C
B
A
N N
N
TBS
O
NHBoc
OBz
OAc
OBz
OAc
OBz
b
1-{2-O-Benzoyl-4,6-O-benzylidene-3-O-[2-O-acetyl-4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylide
ne-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-O-(prop-2-yn-1-yl)-!-D-glucopyranosy
l]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-4-N-(tert-butoxy
carbonyl)aminomethyl-1H-1,2,3-triazole (25)
To a stirred solution of 1alkynylsilane 24 (302 mg, 143 µmol, 1.00 eq.) in THF (4.30 mL) was added
TBAF (214 µL, 1.00 M solution in THF, 214 µmol, 1.50 eq.) at 0 °C. After being stirred at room
temperature for 30 min, the reaction mixture was poured into H2O. The aqueous layer was extracted with two
portions of ethyl acetate. The combined extract was washed with brine, dried over MgSO4, and evaporated
in vacuo. The residue was purified by column chromatography on silica gel with 92:8 toluene:acetone to
give terminal acetylene 25 (276 mg, 138 µmol, 96%).
Rf = 0.53 (toluene/ethyl acetate = 2/1).
["]D33 = -29.5 (c = 0.780, CHCl3).
1H NMR (400 MHz, CDCl3) # 7.10-8.14 (m, 46H, aromatic), 5.83 (d, 1H, H-A1, J = 9.8 Hz), 3.08-5.61 (m,
42H), 2.02 (t, 1H, CCH, J = 2.4 Hz), 1.70 (s, 3H, COCH3), 1.62 (s, 3H, COCH3), 1.47 (s, 9H, Boc).
13C NMR (100 MHz, CDCl3) # 169.1, 169.0, 166.0, 164.9, 164.8, 164.7, 164.2, 137.8, 137.0, 136.8, 133.9,
133.7, 133.3, 132.8, 129.8, 129.7, 129.5, 129.4, 129.2, 129.0, 128.8, 128.5, 128.3, 128.2, 128.0, 127.8, 126.3,
126.1, 125.9, 125.2, 101.6, 100.3, 98.0, 97.7, 86.2, 79.3, 79.1, 78.0, 77.7, 74.9, 74.5, 74.3, 73.2, 71.8, 71.7,
71.0, 69.9, 68.5, 68.4, 68.0, 65.9, 65.1, 63.1, 59.2, 28.4, 21.4, 20.4, 20.3.
FT-IR (neat) 2976, 2872, 1734, 1603, 1496, 1452, 1373, 1316, 1266, 1178, 1097, 1028, 916, 753, 712 cm-1.
HRMS (ESI-TOF) calcd for C108H107N4O34 [M+H]+ 2003.6767, found 2003.6766.

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
Ph
O
Ph
O
Ph
O
BzO
BzO
Ph
O
O
O
O
O
O
O
O
O
O
O
O
O
a
O
E
D
C
B
A
N N
N
O
NHBoc
OBz
OAc
OBz
OAc
OBz
b
1-(2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2-O-benzoyl-4,6-O-benzylide
ne-3-O-(2-O-acetyl-4,6-O-benzylidene-3-O-{2,4,6-tri-O-benzoyl-3-O-[({2-O-benzoyl-4,6-O-benzylidene-3-
O-[2-O-acetyl-4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-acetyl-4,6-O-benzyliden
e-3-O-[2,4,6-tri-O-benzoyl-3-O-(prop-2-yn-1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyr
anosyl)-!-D-glucopyranosyl]-!-D-glucopyranosy}-1H-1,2,3-triazol-4-yl)methyl]-!-D-glucopyranosyl}-!-
D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-4-N-(tert-butoxycarb
onyl)aminomethyl-1H-1,2,3-triazole (27)
A mixture of the terminal acetylene 25 (276 mg, 138 µmol, 96%). (89.2 mg, 0.0445 mmol, 1.00 eq.)
and glycosyl azide 6 (95.8 mg, 0.0488 mmol, 1.10 eq.) in H2O (1.23 mL) and CH2Cl2 (1.50 mL) was added
Na ascorbate (0.178 mL, 0.500 M solution in H2O, 0.0890 mmol, 2.00 eq.) and CuSO4 (0.0890 mL, 0.500 M
solution in H2O, 0.0445 mmol, 1.00 eq.) at room temperature. After being stirred at the same temperature
for 5 h, the reaction mixture was poured into saturated aq. NaHCO3. The aqueous layer was extracted with
two portions of ethyl acetate. The combined extract was washed with 1 M HCl and brine, dried over MgSO4,
and evaporated in vacuo. The residue was used for the next reaction without further purification.
To a stirred solution of the residue in THF (1.50 mL) was added TBAF (73.0 µL, 1.00 M solution in THF,
66.8 µmol, 1.50 eq.) at 0 °C. After being stirred at room temperature for 1 h, the reaction mixture was
poured into H2O. The aqueous layer was extracted with two portions of ethyl acetate. The combined extract
was washed with brine, dried over MgSO4, and evaporated in vacuo. The residue was purified by column
chromatography on silica gel with 90:10 toluene:acetone to give the terminal acetylene 27 (139 mg, 36.0 µmol,
2 steps 81%).
Rf = 0.30 (toluene/acetone = 4/1).
["]D36 = -33.3 (c = 1.39, CHCl3).
1H NMR (400 MHz, CDCl3) # 7.09-8.13 (m, 92H, aromatic), 5.83 (d, 1H, H-A1, J = 9.3 Hz), 3.03-5.62 (m,
83H), 2.02 (t, 1H, CCH, J = 2.4 Hz), 1.72 (s, 3H, COCH3), 1.68 (s, 3H, COCH3), 1.62 (s, 3H, COCH3), 1.60 (s,
3H, COCH3), 1.47 (s, 9H, Boc).
13C NMR (100 MHz, CDCl3) # 169.1, 169.0, 168.9, 166.0, 165.9, 164.9, 164.8, 164.7, 164.1, 145.3, 137.1,
136.8, 133.6, 133.2, 132.8, 129.8, 129.6, 129.5, 129.4, 129.1, 129.0, 128.8, 128.5, 128.4, 128.3, 128.1, 128.0,
127.8, 126.3, 126.1, 125.9, 100.8, 100.3, 98.4, 97.9, 97.5, 86.2, 80.7, 79.2, 79.1, 78.0, 77.8, 77.6, 77.2, 76.5,
75.4, 74.9, 74.2, 73.1, 71.8, 71.7, 71.6, 71.0, 69.8, 68.5, 68.4, 67.9, 65.9, 65.3, 65.0, 63.1, 59.2, 28.3, 20.3,
20.2.
FT-IR (neat) 2873, 1733, 1603, 1494, 1452, 1373, 1316, 1265, 1178, 1096, 915, 751, 712 cm-1.

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
HRMS (ESI-TOF) calcd for C208H200N7O66 [M+H]+ 3851.2509, found 3851.2561.
Ph
O
Ph
O
BzO
BzO
Ph
O
Ph
O
O
O
O
O
O
O
O
O
O
O
O
O
O
N N
N
O
NHBoc
OBz
OAc
OBz
OAc
OBz
N
N N
OBz
OAc
OBz
OAc
OBz
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OBz
OBz
Ph
O
Ph
Ph
O
O
O
Ph
1-[2-O-benzoyl-4,6-O-benzylidene-3-O-(2-O-acetyl-4,6-O-benzylidene-3-O-{2-O-benzoyl-4,6-O-benzylide
ne-3-O-[2-O-acetyl-4,6-O-benzylidene-3-O-(2,4,6-tri-O-benzoyl-3-O-{[(2-O-benzoyl-4,6-O-benzylidene-3-
O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2-O-benzoyl-4,6-O-benzylidene-3-O-(2-O-acetyl-4,6-O-benzyliden
e-3-O-{2,4,6-tri-O-benzoyl-3-O-[({2-O-benzoyl-4,6-O-benzylidene-3-O-[2-O-acetyl-4,6-O-benzylidene-3-
O-(2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-O-(pro
p-2-yn-1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-D-gl
ucopyranosy}-1H-1,2,3-triazol-4-yl)methyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyrano
syl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-1H-1,2,3-triazol-4-yl]methyl}-!-D-glucopyranosyl)-!-D-gl
ucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosy]-4-N-(tert-butoxycarbonyl)
aminomethyl-1H-1,2,3-triazole (28)
A mixture of terminal acetylene 28 (53.4 mg, 13.9 µmol, 1.00 eq.) and the glycosyl azide 6 (29.9 mg,
15.3 µmol, 1.10 eq.) in H2O (2.00 mL) and CH2Cl2 (2.00 mL) was added Na ascorbate (56.0 µL, 0.500 M
solution in H2O, 28.0 µmol, 2.00 eq.) and CuSO4 (28 µL, 0.500 M solution in H2O, 14.0 µmol, 1.00 eq.) at
room temperature. After being stirred at the same temperature for 2 d, the reaction mixture was poured into
saturated aq. NaHCO3. The aqueous layer was extracted with two portions of ethyl acetate. The combined
extract was washed with 1 M HCl and saturated aq. NaHCO3 and brine, dried over MgSO4, and evaporated in
vacuo. The residue was used for the next reaction without further purification.
To a stirred solution of the residue in THF (1.00 mL) was added TBAF (15.0 µL, 1.00 M solution in
THF, 15.0 µmol, 1.10 eq.) at 0 °C. After being stirred at room temperature for 1 h, the reaction mixture was
poured into H2O. The aqueous layer was extracted with two portions of ethyl acetate. The combined extract
was washed with brine, dried over MgSO4, and evaporated in vacuo. The residue was purified by GPC to give
terminal acetylene 28 (49.6 mg, 8.70 µmol, 2 steps 63%).
Rf = 0.33 (toluene/acetone = 3/1).
["]D29 = -35.0 (c = 0.990, CHCl3).
1H NMR (400 MHz, CDCl3) # 7.09-8.13 (m, 138H, aromatic), 5.83 (d, 1H, H-A1, J = 9.3 Hz), 3.00-5.62 (m,
124H), 2.02 (t, 1H, CCH, J = 2.0 Hz), 1.72 (s, 3H, COCH3), 1.69 (s, 3H, COCH3), 1.69 (s, 3H, COCH3), 1.65
(s, 3H, COCH3), 1.61 (s, 3H, COCH3), 1.60 (s, 3H, COCH3), 1.47 (s, 9H, Boc).

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
FT-IR (neat) 2875, 1732, 1602, 1493, 1452, 1374, 1316, 1265, 1178, 1070, 1027, 913, 802, 753, 712, 532
cm-1.
HRMS (ESI-TOF) calcd for C308H293N10O98 [M+H]+ 5698.8251, found 5698.8438.
Ph
O
Ph
O
BzO
BzO
Ph
O
Ph
O
O
O
O
O
O
O
O
O
O
O
O
O
O
N N
N
O
NHBoc
OBz
OAc
OBz
OAc
OBz
N
N N
OBz
OAc
OBz
OAc
OBz
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OBz
Ph
O
Ph
Ph
O
O
Ph
O
OBz
Ph
O
BzO
BzO
Ph
O
Ph
O
Ph
O
O
O
O
O
O
O
O
O
O
O
O
O
O
H
O
N
N
OBz
N
OAc
OBz
OAc
OBz
1-[3-O-(3-O-{3-O-[3-O-(2,4,6-tri-O-benzoyl-3-O-{[(3-O-{3-O-[3-O-(3-O-{-O-[({3-O-[3-O-(3-O-{3-O-[3-O-(
prop-2-yn-1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-
D-glucopyranosy}-1H-1,2,3-triazol-4-yl)methyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyr
anosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-1H-1,2,3-triazol-4-yl]methyl}-!-D-glucopyranosyl)-!-
D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosy]-4-N-(tert-butoxycarb
onyl)aminomethyl-1H-1,2,3-triazole (3)
To a stirred solution of the protected oligosaccahride (28) (29.8 mg, 5.23 µmol, 1.00 eq.) in CH2Cl2
(970 µL) was added trifluoroacetic acid (30.0 µL) and a catalytic amount of H2O at 0 °C. After being stirred
at room temperature for 3 h, the reaction mixture was neutralized with triethylamine and evaporated in vacuo.
The residue was used for the next reaction without further purification.
To a stirred solution of the residue in MeOH (4.00 mL) and THF (4.00 mL) was added a catalytic
amount of NaOMe at room temperature. After being stirred at the same temperature for 2 d, the reaction
mixture was neutralized with DOWEX 50W-X2 and filtered through a pad of Celite. The filtrate mixture
was evaporated in vacuo. The residue was purified by reverse-phase column chromatography (Bond
Elut-C18) to give the trimer of the pentasaccharide (3) (5.40 mg, 1.98 µmol, 2 steps 38%).
Rf = 0.00 (acetic acid/n-butanol/H2O = 4/4/1).
["]D25 = -5.19 (c = 0.270, H2O).
1H NMR (400 MHz, D2O) # 8.44 (s, 1H, aromatic), 8.29 (s, 1H, aromatic), 8.11 (s, 1H, aromatic), 5.75-5.81
(m, 3H), 3.34-5.07 (m, 110H).
FT-IR (neat) 3860, 3821, 3780, 3762, 3410, 3310, 3290, 3277, 3250, 2906, 2528, 1965, 1593, 1378, 1050,

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
905, 598 cm-1.
HRMS (ESI-TOF) calcd for C102H165N10O75 [M+H]+ 2729.9405, found 2729.9482.
HO
HO
HO
HO
O
HO
HO
O
HO
HO
O
HO
HO
O
O
N N
N
O
O
O
O
O
NH2
OH
OH
OH
OH
OH
OH
N
N N
OH
OH
OH
OH
O
O
O
O
O
O
O
OH
OH
O
O
O
OH
OH
OH
OH
OH
OH
OH
OH
HO
HO
HO
HO
HO
O
HO
HO
O
HO
HO
HO
O
O
O
O
O
O
O
O
N
N
OH
N
OH
OH
OH
OH

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
1-[2,4,6-Tri-O-benzoyl-3-O-(3-tert-butyldimethylsilyl-prop-2-yn-1-yl)-!-D-glucopyranosyl]-4-phenyl-1H-
1,2,3-triazole(11)
BzO
BzO
O
a
N N
R
N
O
Ph
BzO
b

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
1-[2,4,6-Tri-O-benzoyl-3-O-(prop-2-yn-1-yl)-!-D-glucopyranosyl]-4-phenyl-1H-1,2,3-triazole (12)
BzO
BzO
a
O
N N
N
O
Ph
BzO
b

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2,4,6-Tri-O-benzoyl-3-O-{1-[2,4,6-tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!-D-gluco
pyranosyl]-1H-1,2,3-triazol-4-yl}methyl-!-D-glucopyranosyl 4-phenyl-1H-[1,2,3]triazole (13)
BzO
BzO
BzO
a
BzO
b
O
O
B
N N
A
TBS
N N
N
O
O
N
Ph
OBz
c'
OBz
c

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
1,2,5,6-Bis-O-isopropylidene-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-"-D-glucofuranose (15)
O
O
O
O
H
O
O
a
TBS

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
1,2,4,6-Tetra-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-"/!-D-glucopyranose (16)
BzO
BzO
O
TBS
O
OBz
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2,4,6-Tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-D-glucopyranose (17)
BzO
BzO
O
TBS
O
OH
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
O-[2,4,6-Tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!,"-D-glucopyranosyl]
trichloroacetimidate (6)
BzO
BzO
O
TBS
O
O
NH
CCl3
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
Ethylthio 2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-ꢀ
O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranos
ide (20)
BzO
O
Ph
O
O
Ph
O
BzO
O
O
O
O
O
a
B
A
TBS
O
SEt
OBz
OAc
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2-O-Benzoyl-4,6-O-benzylidene-3-O-(4,6-O-benzylidene-2,3-di-O-levulinoyl-!-D-glucopyranosyl)-!-D-glu
copyranosyl azide (21)
O
Ph
O
O
Ph
O
O
O
O
O
O
N3
O
OBz
O
O
O

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2-O-Benzoyl-4,6-O-benzylidene-3-O-(4,6-O-benzylidene-!-D-glucopyranosyl)-!-D-glucopyranosyl azide
(22)
O
Ph
O
Ph
O
O
O
O
O
HO
N3
OH
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2-O-Benzoyl-4,6-O-benzylidene-3-O-[4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylidene-3-O-{2-O-
acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-1-yl)-!-D-glu
copyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-D-glucopyranosyl azide
(23)
BzO
BzO
O
Ph
O
O
O
Ph
O
Ph
O
O
Ph
O
O
O
O
O
O
O
O
O
O
a
E
D
C
A
B
TBS
O
N3
OBz
OBz
OH
OBz
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
2-O-Benzoyl-4,6-O-benzylidene-3-O-(2-O-acetyl-4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylidene
-3-O-(2-O-acetyl-4,6-O-benzylidene-3-O-(2,4,6-tri-O-benzoyl-3-O-(prop-3-tert-butyldimethylsilyl-2-yn-1-
yl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyranosyl)-!-D-glucopyran
osyl azide (4)
BzO
O
Ph
O
O
O
Ph
O
Ph
O
O
Ph
O
BzO
O
O
O
O
O
O
O
O
O
a
E
D
C
A
B
TBS
O
N3
OBz
OBz
OAc
OBz
OBz

ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
1-{2-O-Benzoyl-4,6-O-benzylidene-3-O-[2-O-acetyl-4,6-O-benzylidene-3-O-(2-O-benzoyl-4,6-O-benzylide
ne-3-O-{2-O-acetyl-4,6-O-benzylidene-3-O-[2,4,6-tri-O-benzoyl-3-O-(3-tert-butyldimethylsilylprop-2-yn-
1-yl)-!-D-glucopyranosyl]-!-D-glucopyranosyl}-!-D-glucopyranosyl)-!-D-glucopyranosyl]-!-D-glucopyr
anosyl}-4-N-(tert-butoxycarbonyl)aminomethyl-1H-1,2,3-triazole (24)
Ph
O
Ph
Ph
BzO
BzO
Ph
O
O
O
O
O
O
O
O
O
O
O
O
O
O
a
O
O
E
D
C
B
A
N N
N
TBS
O
NHBoc
OBz
OAc
OBz
OAc
OBz
b