Desde Acetilado Con TMSN3-FeCl3

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2011
S1
Iron (III) Chloride as an Efficient Catalyst for Stereoselective

Synthesis of Glycosyl Azides and a Cocatalyst with Cu(0) for the
Subsequent Click Chemistry
Santosh B. Salunke,b,c N.Seshu Babua,c and Chien-Tien Chena∗

a
Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan
b
National Taiwan Normal University, Taipei, Taiwan
c
Santosh B.Salunke and N.Seshu Babu made equal contributions to this work
e-mail: ctchen@mx.nthu.edu.tw
SUPPORTING INFORMATION
Detailed procedures for FeCl3 catalyzed azido glycosylation and analytical data of
azido glycosides 1-10; Detailed procedures for FeCl3:Cu catalyzed dipolar
cycloaddition and analytical data for glycosyl 1,2,3-triazole conjugates 11-16;
procedure for one pot synthesis of 17; 1H and 13C NMR spectra for 1-17 (63 pages).
Table of Content
General experimental methods, Caution, and Attention------------------------------S2-S3
Table S1: Effect of solvents on the azido glycosylation of β-glucose peracetate------S4
Detailed procedure for FeCl3 catalyzed azido glycosylation and analytical data for
azido glycosides 1-10--------------------------------------------------------------------S4-S18
Table S2: Optimization of FeCl3/Cu(0) ratio for cyclo-addition reaction (i. e. click
chemistry) between β-azido glucose and 2-phenylethyne-------------------------------S19
Table S3: Control experiments for cycloaddition reactions between β-azido glucose
and 2-phenylethyne by using Sharpless and Fokin’s reagents--------------------S19-S20
Table S4: Control experiments for cycloaddition reactions between β-azido glucose
and 2-phenylethyne by using bimetallic catalyst Cu(OTf)2:Cu system----------------S20
S2
Detailed procedure for FeCl3:Cu catalyzed dipolar cycloaddition and analytical data
for glycosyl 1,2,3-triazole conjugates 11-16-----------------------------------------S20-S29
Procedure for one pot synthesis of glycosyl 1,2,3-triazole conjugate 17------- S29-S31
References------------------------------------------------------------------------------- S31-S33
1
H and 13C NMR spectra’s for 1-17---------------------------------------------------S34-S67
General. 1H NMR and 13

C NMR spectra were recorded on 400 MHz 1H (100 MHz
13
C) spectrometers in deuterochloroform with chloroform as an internal reference
unless otherwise stated. Chemical shifts are reported in ppm (δ). Coupling constants,
J, are reported in Hz. Electrospray ionization (ESI) mass spectra were recorded with
data reported in the form m/e (intensity relative to base peak). Analytical TLC was
performed on silica gel glass plates. Visualization was accomplished with UV light or
with phosphomolybdic acid (PMA) and KMnO4 staining agents. Column (flash)
chromatography was performed using 32-63 μm silica gels. THF and toluene were
dried over Na with benzophenone-ketyl intermediate under nitrogen atmosphere and
distilled before use. DMF, CH2Cl2 and CHCl3 were dried over CaH and distilled
before use. MeOH was dried over magnesium turnings under nitrogen atmosphere and
distilled before use. Oxygen was purged in CHCl3 before use. All reaction products
were isolated as chromatographically pure materials. All reagents and catalysts used
for azido glycosylation reaction were purchased from Across Organics. The acetate
S3
derivatives of glucose1, glactose2, mannose3, ribose, xylose4, maltose, lactose5,
maltotriose6 were synthesized by using 2 equiv of acetic anhydride (for each hydroxyl
group) in the presence of 10 mol% of Sodium acetate under reflux condition.
N-protected glucosamine derived substrates and propargyl-O-linked glucose
peracetate7 were synthesized by using literature methods.
Caution: Organic azides (e.g. TMSN3) are potentially explosive and corrosive
compounds and should be handled with great care,8 despite we did not sense any
adverse effects during our studies at small scale reactions.
Attention: It has been documented in the literatures that, ionic azides react with
CH2Cl2 to form explosive azidochloromethane and/or diazidomethane.9 It has been
noted that, if these azides were formed, they would be converted to stable triazole
derivatives in the subsequent azide-alkyne cycloaddition reactions. However, we did
not observe these side products under our catalytic conditions.

S4
Table S1. Effect of solvents on the azido glycosylation of glucose β-peracetate.a

OAc OAc
5 mol% FeCl3
AcO O OAc TMSN3 AcO O N3
AcO Solvent (1 mL) AcO
OAc OAc
1
Entry Solvent Time (h) Conversion (%)b Yield (%)c

1 CH3CN 36 5 n.d.
2 CH3COCH3 36 0 --
3 CH3NO2 36 decomposed --
4 THF 36 0 --
5 TBME 40 55 47
6 toluene 40 95 86
d
7 toluene 7 quantitative 91
8 CH2Cl2 6 quantitative 96
a
Carried out by using TMSN3 (0.38 mmol, 1.5 equiv), 5 mol% FeCl3 catalyst in 1
mL of solvent. bConversion of β-D-glucose peracetate was determined by 1H NMR
analysis of the crude reaction mixture. cIsolated, purified yield. dReaction was
conducted at 70 °C .
(A) Detailed procedures for FeCl3 catalyzed azido glycosylation and analytical
data of azido glycosides 1-10.
2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-glucopyranosyl azide (1).10
To a 10 mL, round bottomed flask was placed 5 mol% of FeCl3 (2 mg, 0.0125 mmol,
0.05 equiv) in anhydrous CH2Cl2 (0.5 mL) under nitrogen atmosphere. A solution of
(2S,3R,4S,5R,6R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate
(97.5 mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been
S5
stirred for 5 min at ambient temperature, a solution of trimethyl silyl azide i.e. TMSN3
(50 μL, 44 mg, 0.38 mmol, 1.5 equiv) in CH2Cl2 (0.25 mL) was added slowly. The
resulting reaction mixture was stirred at ambient temperature and the progress of the
reaction was monitored by TLC. After complete consumption of starting material in 6
h, the reaction mixture was quenched with saturated aqueous NaHCO3 solution (5
mL). Two layers were separated and the aqueous layer was extracted with CH2Cl2 (2
× 3 mL). The combined organic layers were washed with brine (5 mL), dried
(MgSO4), filtered and evaporated under reduced pressure. The crude reside was
purified by column chromatography (EtOAc/hexanes, 1/2) on silica gel to afford 89
mg (96%) of 2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-glucopyranosyl azide 1 as a white
solid. 1H NMR (400 MHz, CDCl3) δ 5.19 (t, J = 9.2, 1H), 5.07 (t, J = 10, 1H), 4.92 (t,
J = 9.2, 1H), 4.63 (d, J = 8.8, 1H), 4.25 (dd, J = 12.4, 4.8, 1H), 4.14 (dd, J = 12.4, 2,
1H), 3.80-3.76 (m, 1H), 2.07 (s, 3H, COCH3), 2.05 (s, 3H, COCH3), 2.00 (s, 3H,
13
COCH3), 1.98 (s, 3H, COCH3); C NMR (100 MHz, CDCl3) δ 170.5, 170.0, 169.2,
169.1, 87.8, 74.0, 72.5, 70.6, 67.9, 61.6, 20.6, 20.4; MS ESI (C14H19O9N3, 373): 396
(M+Na+, 100); TLC Rf 0.34 (EtOAc/hexanes, 1/2); m.p. 124-125 °C (lit.11 m.p. 127
°C); [α]25D -30.2 (c 1.0, CHCl3) (lit.10 [α]23D -31 (c 1.0, CHCl3)).
S6
2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-galactopyranosyl azide (2).10
To a 10 mL, round bottomed flask was placed 5 mol% of FeCl3 (2 mg, 0.0125
mmol, 0.05 equiv) in anhydrous CH2Cl2 (0.5 mL) under nitrogen atmosphere. A
solution of (2S,3S,4S,5R,6R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl
tetraacetate (97.5 mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After
having been stirred for 5 min at ambient temperature, a solution of TMSN3 (50 μL, 44
mg, 0.38 mmol, 1.5 equiv) in CH2Cl2 (0.25 mL) was added slowly. The resulting
reaction mixture was stirred at ambient temperature and the progress of the reaction
was monitored by TLC. After complete consumption of starting material in 6 h, the
reaction mixture was quenched with saturated aqueous NaHCO3 solution (5 mL). Two
layers were separated and the aqueous layer was extracted with CH2Cl2 (2 × 3 mL).
The combined organic layers were washed with brine (5 mL), dried (MgSO4), filtered
and evaporated under reduced pressure. The crude reside was purified by column
chromatography (EtOAc/hexanes, 1/2) on silica gel to afford 89 mg (96%) of
2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-galactopyranosyl azide 2 as a white solid. 1H
NMR (400 MHz, CDCl3) δ 5.41 (d, J = 2.4, 1H), 5.15 (dd, J = 10, 8.8, 1H), 5.02 (dd,
J = 10.4, 3.6, 1H), 4.59 (d, J = 8.8, 1H), 4.18-4.14 (m, 2H), 4.00 (td, J = 6.8, 0.6, 1H),
S7
2.16 (s, 3H, COCH3), 2.08 (s, 3H, COCH3), 2.05 (s, 3H, COCH3), 1.98 (s, 3H,
COCH3); 13C NMR (100 MHz, CDCl3) δ 170.3, 170.0, 169.9, 169.2, 88.1, 72.7, 70.6,
67.95, 66.8, 61.2, 20.5, 20.4, 20.35; MS ESI (C14H19O9N3, 373): 396 (M+Na+, 100);
TLC Rf 0.35 (EtOAc/hexanes, 1/2); m.p. 95-97 °C (lit.11 m.p. 94-95 °C); [α]25D -15.4 (c
1.0, CHCl3) (lit.10 [α]23D -14 (c 1.0, CHCl3)).
2,3,4,6-tetra-O-acetyl-6-deoxy-α-D-mannopyranosyl azide (3).12
AcO OAc AcO OAc

5 mol% FeCl3
AcO O TMSN3 AcO O
AcO OAc CH2Cl2 (1 mL) AcO
rt, 7 h N3
3
To a 10 mL, round bottomed flask was placed 5 mol% of FeCl3 (2 mg, 0.0125
solution of (3S,4S,5S,6R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl
tetraacetate (97.5 mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After
having been stirred for 5 min at ambient temperature, a solution of TMSN3 (50 μL, 44
mg, 0.38 mmol, 1.5 equiv) in CH2Cl2 (0.25 mL) was added slowly. The resulting
S8
2,3,4,6-tetra-O-acetyl-6-deoxy-α-D-mannopyranosyl azide 3 as a white solid. 1H
NMR (400 MHz, CDCl3) δ 5.37 (d, J = 1.5, 1H), 5.28-5.20 (m, 2H), 5.13 (t, J =2.3,
1H), 4.28 (dd, J = 12.4, 5.5, 1H), 4.16-4.11 (m, 2H), 2.18 (s, 3H, COCH3), 2.14 (s, 3H,
13
COCH3), 2.1 (s, 3H, COCH3), 2.05 (s, 3H, COCH3); C NMR (100 MHz, CDCl3)
δ 170.5, 169.8, 169.7, 169.6, 87.4, 70.6, 69.1 68.2, 65.6, 62.1, 20.7, 20.61, 20.6, 20.5;
MS ESI (C14H19O9N3, 373): 396 (M+Na+, 100); TLC Rf 0.32 (EtOAc/hexanes, 1/2).
m.p. 103-105 °C (lit.13 m.p. 104.1-104.9 °C); [α]25D +181.1 (c 1.0, CHCl3) (lit.13 [α]23D
+184 (c 1.0, CHCl3)).
2,3,5-tri-O-acetyl-β-D-ribofurunosyl azide (4).14
O OAc 5 mol% FeCl3 O N3

AcO TMSN3 AcO
CH2Cl2 (1 mL)
AcO OAc rt, 1.5 h AcO OAc
4
To a 10 mL, round bottomed flask was placed 5 mol% of FeCl3 (1.2 mg, 0.0075 mmol,
(2S,3R,4R,5R)-5-(acetoxymethyl)tetrahydrofuran-2,3,4-triyl triacetate (79.5 mg, 0.25
mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been stirred for 5 min at
S9
ambient temperature, a solution of TMSN3 (50 μL, 44 mg, 0.38 mmol, 1.5 equiv) in
CH2Cl2 (0.25 mL) was added slowly. The resulting reaction mixture was stirred at
ambient temperature and the progress of the reaction was monitored by TLC. After
complete consumption of starting material in 1.5 h, the reaction mixture was
quenched with saturated aqueous NaHCO3 solution (5 mL). Two layers were
separated and the aqueous layer was extracted with CH2Cl2 (2 × 3 mL). The combined
organic layers were washed with brine (5 mL), dried (MgSO4), filtered and
evaporated under reduced pressure. The crude reside was purified by column
2,3,5-tri-O-acetyl-β-D-ribofurunosyl azide 4 as a colorless oil. 1H NMR (400 MHz,
CDCl3) δ 5.33 (d, J = 1.4, 1H), 5.30 (dd, J = 6.6, 5.0, 1H), 5.10 (dd, J = 4.8, 1.6, 1H),
4.38 (dd, J = 12, 3.2, 1H), 4.34-4.30 (m, 1H), 4.12 (dd, J = 12.2, 4.2, 1H), 2.092 (s,
13
3H, COCH3), 2.09 (s, 3H, COCH3), 2.04 (s, 3H, COCH3); C NMR (100 MHz,
CDCl3) δ 170.5, 169.5, 169.3, 92.6, 79.3, 74.4, 70.4, 62.9, 20.6, 20.4, 20.3; MS ESI
(C11H15O7N3, 301): 324 (M+Na+, 100); TLC Rf 0.34 (EtOAc/hexanes, 1/2); [α]25D
+111.3 (c 1.0, CHCl3) (lit.14 [α]23D +116 (c 1.0, CHCl3)).

S10
2,3,5-tri-O-acetyl-β-D-xylopyranosyl azide (5).10
To a 10 mL, round bottomed flask was placed 5 mol% of FeCl3 (1.2 mg, 0.0075
solution of (2S,3S,4S)-tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (79.5 mg, 0.25
mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been stirred for 5 min at
ambient temperature, a solution of TMSN3 (50 μL, 44 mg, 0.38 mmol, 1.5 equiv) in
CH2Cl2 (0.25 mL) was added slowly. The resulting reaction mixture was stirred at
complete consumption of starting material in 3 h, the reaction mixture was quenched
with saturated aqueous NaHCO3 solution (5 mL). Two layers were separated and the
aqueous layer was extracted with CH2Cl2 (2 × 3 mL). The combined organic layers
were washed with brine (5 mL), dried (MgSO4), filtered and evaporated under
reduced pressure. The crude reside was purified by column chromatography
(EtOAc/hexanes, 1/2) on silica gel to afford 69 mg (92%) of 2,3,5-tri-O-acetyl-β-D-
xylopyranosyl azide 5 as a white solid. 1H NMR (400 MHz, CDCl3) δ 5.18 (t, J = 8.8,
1H), 5.00-4.95 (m, 1H), 4.87 (t, J = 8.4, 1H), 4.63 (d, J = 8.0, 1H), 4.21 (dd, J = 12,
5.6, 1H), 3.44 (dd, J = 11.6, 9.2, 1H), 2.07 (s, 3H, COCH3), 2.042 (s, 3H, COCH3),
2.04 (s, 3H, COCH3); 13C NMR (100 MHz, CDCl3) δ 169.9, 169.7, 169.3, 88.3, 71.5,
S11
70.4, 68.4, 64.3, 20.6, 20.6; MS ESI (C11H15O7N3, 301): 324 (M+Na+, 100); TLC Rf
0.34 (EtOAc/hexanes, 1/2); m.p. 84-85 °C (lit.15 m.p. 87 °C); [α]25D +88.4 (c 1.0,
CHCl3) (lit.15 [α]25D +86 (c 1.0, CHCl3)).
2,3,6-tri-O-acetyl-4-O-( 2’,3’,4’,6’-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-glu-
copyranosylazide (6).10
(2S,3S,4S,6R)-6-(acetoxymethyl)-5-((2S,3S,4S,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)
tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2,3,4-triyl triacetate (169.5 mg,
0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been stirred for 5
min at ambient temperature, a solution of TMSN3 (50 μL, 44 mg, 0.38 mmol, 1.5
equiv) in CH2Cl2 (0.25 mL) was added slowly. The resulting reaction mixture was
stirred at ambient temperature and the progress of the reaction was monitored by TLC.
After complete consumption of starting material in 24 h, the reaction mixture was
S12
2,3,6-tri-O-acetyl-4-O-(2’,3’,4’,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-glucopyr
-anosyl azide 6 as a amorphous solid. 1H NMR (400 MHz, CDCl3) δ 5.34 (d, J = 3.6,
1H), 5.20 (t, J = 9.4, 1H), 5.09 (dd, J = 10.4, 8, 1H), 4.94 (dd, J = 10.4, 3.6, 1H), 4.85
(t, J = 9.6, 1H), 4.62 (d, J = 8.8, 1H), 4.52-4.46 (m, 2H), 4.14-4.05 (m, 3H), 3.87 (t, J
= 6.8, 1H), 3.81 (t, J = 9.6, 1H), 3.70-3.71 (m, 1H), 2.14 (s, 3H, COCH3), 2.13 (s, 3H,
COCH3), 2.08 (s, 3H, COCH3), 2.06 (s, 3H, COCH3), 2.05 (s, 3H, COCH3), 2.04 (s,
13
3H, COCH3), 1.95 (s, 3H, COCH3); C NMR (100 MHz, CDCl3) δ 170.3, 170.1,
170.0, 169.6, 169.5, 169.1, 101.1, 87.7, 75.7, 74.8, 72.5, 71.0, 70.9, 70.7, 69.0, 66.6,
61.7, 60.8, 20.8, 20.7, 20.6, 20.5; MS ESI (C26H35O17N3, 661): 684 (M+Na+, 100);
TLC Rf 0.20 (EtOAc/hexanes, 1/1); [α]25D -21.2 (c 1.0, CHCl3) (lit.10 [α]23D -20.4 (c 1.0,
CHCl3)).
2,3,6-tri-O-acetyl-4-O-(2’,3’,4’,6’-tetra-O-acetyl-β-D-glucopyranosyl)-β-D-glucop
yranosylazide (7).10
S13
(2S,3S,4S,5R,6R)-6-(acetoxymethyl)-5-((3S,4S,5S,6R)-3,4,5-triacetoxy-6-(acetoxymet
hyl)tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2,3,4-triyl triacetate (169.5 mg,
0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been stirred for 5
min at ambient temperature, a solution of TMSN3 (50 μL, 44 mg, 0.38 mmol, 1.5
equiv) in CH2Cl2 (0.25 mL) was added slowly. The resulting reaction mixture was
2,3,6-tri-O-acetyl-4-O-(2’,3’,4’,6’-tetra-O-acetyl-β-D-glucopyranosyl)-β-D-glucopyra
-nosyl azide 7 as a white solid. 1H NMR (400 MHz, CDCl3) δ 5.40 (d, J = 4, 1H), 5.35
(t, J = 10, 1H), 5.26 (t, J = 9.0, 1H), 5.05 (t, J = 9.8, 1H), 4.85 (dd, J = 10.8, 4.0, 1H),
4.78 (t, J = 8.8, 1H), 4.70 (d, J = 8.8, 1H), 4.51 (dd, J = 12, 2.4, 1H), 4.26-4.24 (m,
12.4, 2H), 4.07-4.03 (m, 2H), 4.01-3.99 (m, 1H), 3.79-3.70 (m, 1H), 2.15 (s, 3H,
13
S14
CDCl3) δ 170.4, 170.3, 169.9, 169.8, 169.3, 169.3, 95.6, 77.3, 77.0, 76.7, 74.9, 72.3,
71.4, 69.9, 69.1, 68.5, 67.9, 62.4, 61.4, 20.7, 20.6, 20.5, 20.4; MS ESI (C26H35O17N3,
661): 684 (M+Na+, 100); TLC Rf 0.15 (EtOAc/hexanes, 1/1); m.p. 181-183 °C (lit.16a
m.p. 180-182 °C); [α]25D -32.1 (c 1.0, CHCl3) (lit.16b [α]24D -31 (c 1.0, CHCl3)).
2,3,4,6-tetra-O-acetyl-6-deoxy-α-D-glucopyranosyl-(1-4)-2,3,6-tri-O-acetyl-6-deo
xy-α-D-glucopyranosyl-(1-4)-2,3,6-tri-O-acetyl-6-deoxy-β-D-glucopyranosyl
azide (8).17
OAc OAc
AcO O AcO O
AcO OAc 5 mol% FeCl3 AcO OAc
AcO TMSN3 AcO
O O O O
OAc CH2Cl2 (1 mL) OAc
AcO AcO
AcO rt, 28 h AcO
O O O O
AcO OAc AcO N3
AcO AcO
8
(2S,3R,4S,5R,6R)-6-(acetoxymethyl)-5-((2R,3R,4S,5R,6R)-3,4-diacetoxy-6-(acetoxym
ethyl)-5-((2R,3R,4S,5R,6R)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2
-yloxy)tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2,3,4-triyl triacetate (241.5
mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been stirred
for 5 min at ambient temperature, a solution of TMSN3 (50 μL, 44 mg, 0.38 mmol,
1.5 equiv) in CH2Cl2 (0.25 mL) was added slowly. The resulting reaction mixture was

S15
2,3,4,6-tetra-O-acetyl-6-deoxy-α-D-glucopyranosyl-(1-4)-2,3,6-tri-O-acetyl-6-deoxy-
α-D-glucopyranosyl-(1-4)-2,3,6-tri-O-acetyl-6-deoxy-β-D-glucopyranosyl azide 8 as
a white solid. 1H NMR (400 MHz, CDCl3) δ 5.37-5.32 (m, 2H), 5.32 (d, J = 6.4, 1H),
5.25-5.21 (m, 2H), 5.03 (t, J = 9.8, 1H), 4.82 (dd, J = 10.4, 4.0, 1H), 4.76-4.67 (m,
3H), 4.49-4.41 (m, 2H), 4.29 (dd, J = 12.2, 4.4, 1H), 4.21 (dd, J = 12.4, 3.6, 1H), 4.15
(dd, J = 12.4, 3.2, 1H), 4.02 (dd, J = 12.4, 2.0, 1H), 3.96 (d, J = 9.2, 1H), 3.93-3.87
(m, 3H), 3.81-3.79 (m, 1H), 2.15 (s, 3H, COCH3), 2.12 (s, 3H, COCH3), 2.06 (s, 3H,
COCH3), 2.02 (s, 3H, COCH3), 2.0 (s, 6H, COCH3), 1.98 (s, 3H, COCH3), 1.97 (s, 6H,
13
2 × COCH3), 1.96 (s, 3H, COCH3); C NMR (100 MHz, CDCl3) δ 170.5, 170.4,
170.3, 170.4, 170.2, 169.7, 169.6, 169.4, 169.3, 95.8, 95.6, 87.3, 74.8, 74.0, 73.4, 72.4,
71.6, 71.4, 70.3, 70.0, 69.2, 69.0, 68.4, 67.8, 62.6, 62.2, 61.3, 20.8, 20.7, 20.5, 20.5,
20.4; MS ESI (C38H51O25N3, 949): 972 (M+Na+, 100); TLC Rf 0.10 (EtOAc/hexanes,
1/1); m.p. 95-96 °C; [α]25D +69.2 (c 1.0, CHCl3) (lit.17b [α]25D +65 (c 1.2, CHCl3)).
S16
3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl azide (9).18
OAc OAc
AcO O AcO O
N3 N3
AcO 5 mol% FeCl3 AcO
O N O TMSN3 O N O
CH2Cl2 (1 mL)
rt, 22 h
(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(1,3-dioxoisoindolin-2-yl)tetrahydro-2H-pyra
n-2,4,5-triyl triacetate (119 mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added.
After having been stirred for 5 min at ambient temperature, a solution of TMSN3 (50
μL, 44 mg, 0.38 mmol, 1.5 equiv) in CH2Cl2 (0.25 mL) was added slowly. The
resulting reaction mixture was stirred at ambient temperature and the progress of the
reaction was monitored by TLC. After complete consumption of starting material in
22 h, the reaction mixture was quenched with saturated aqueous NaHCO3 solution (5
mL). Two layers were separated and the aqueous layer was extracted with CH2Cl2 (2
× 3 mL). The combined organic layers were washed with brine (5 mL), dried
(MgSO4), filtered and evaporated under reduced pressure. The crude reside was
purified by column chromatography (EtOAc/hexanes, 3/2) on silica gel to afford 105
mg (91%) of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl azide 9 as
a white solid. 1H NMR (400 MHz, CDCl3) δ 7.87 (dd, J = 5.4, 3.0, 2H), 7.76 (dd, J =
S17
5.5, 3.0, 2H), 5.80 (dd, J = 10.5, 9.2, 1H), 5.65 (d, J = 9.4, 1H), 5.19 (t, J = 9.7, 1H),
4.35 (dd, J = 4.7, 12.4, 1H), 4.24 (dd, J = 12.5, 2.3, 1H), 4.24 (dd, J = 10.6, 9.2, 1H),
3.99-3.96 (m, 1H), 2.12 (s, 3H, COCH3), 2.03 (s, 3H, COCH3), 1.86 (s, 3H, COCH3);
13
C NMR (100 MHz, CDCl3) δ 170.6, 169.9, 169.3, 134.5, 131.2, 123.7, 73.9, 85.5,
70.4, 68.4, 61.7, 53.1, 20.6, 20.5, 20.3; MS ESI (C20H20O9N4, 460): 483 (M+Na+,
100); TLC Rf 0.28 (EtOAc/hexanes, 1/1); m.p. 135-137 °C (lit.18a m.p. 135-138 °C);
[α]25D +39.6 (c 1.0, CHCl3) (lit.18b [α]25D +38 (c 1.0, CHCl3)).
3,4,6-tri-O-acetyl-2-N-acetyl-2-deoxy-β-D-glucopyranosyl azide (10).10
OAc OAc
20 mol% FeCl3
AcO O OAc TMSN3 AcO O N3
AcO CH2Cl2 (1 mL) AcO
NHAc NHAc
rt, 72 h
10
To a 10 mL, round bottomed flask was placed 5 mol% of FeCl3 (8 mg, 0.05 mmol, 0.2
equiv) in anhydrous CH2Cl2 (0.5 mL) under nitrogen atmosphere. A solution of
(2S,3R,4R,5S,6R)-3-acetamido-6-(acetoxymethyl)tetrahydro-2H-pyran-2,4,5-triyl
triacetate (97 mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having
been stirred for 5 min at ambient temperature, a solution of TMSN3 (50 μL, 44 mg,
0.38 mmol, 1.5 equiv) in CH2Cl2 (0.25 mL) was added slowly. The resulting reaction
mixture was stirred at ambient temperature and the progress of the reaction was
monitored by TLC. After complete consumption of starting material in 72 h, the

S18
3,4,6-tri-O-acetyl-2-N-acetyl-2-deoxy-β-D-glucopyranosyl azide 10 as a white solid.
1
H NMR (400 MHz, CDCl3) δ 6.09 (d, J = 8.8, 1H, NH), 5.25 (t, J = 10, 1H), 5.08 (t,
J = 9.6, 1H), 4.78 (d, J = 9.2, 1H), 4.25 (dd, J = 4.8, 12.4, 1H), 4.16-4.13 (m, 1H),
3.91 (dd, J = 19.4, 9.3, 1H), 3.81 (m, 1H), 2.09 (s, 3H, COCH3), 2.024 (s, 3H,
13
COCH3), 2.02 (s, 3H, COCH3), 1.97 (s, 3H, COCH3); C NMR (100 MHz, CDCl3)
δ 170.9, 170.7, 170.6, 169.3, 88.3, 76.7, 73.9, 72.1, 68.1, 61.9, 54.0, 23.1, 20.7, 20.6,
20.5; MS ESI (C14H20O8N4, 372): 395 (M+Na+, 100); TLC Rf 0.20 (EtOAc/hexanes,
1/1); m.p. 161-162 °C (lit.19 m.p. 158-161 °C); [α] D -45.9 (c 1.0, CHCl3) (lit.10 [α] D
25 23
-47.7 (c 1.0, CHCl3)).

S19
Table S2: Optimization of FeCl3/Cu(0) ratio for cycloaddition reactions (i. e. click
chemistry) between β-azido glucose and 2-phenylethyne.a
Entry FeCl3 Cu powder FeCl3:Cu ratio Time, h Yield (%)

mol% mol%
1 20 0 1:0 48 No reaction
2 0 100 0:1 48 No reaction
3 20 20 1:1 48 No reaction
4 20 30 1:1.5 48 Sluggish reaction
5 20 40 1:2 40 92
6 20 100 1:5 10 94
a
Reaction details: β-azido glucose (0.25 mmol, 1 equiv), 2-phenylethyne (0.375
mmol, 1.5 equiv) in t-BuOH:H2O (2 mL:1 mL). bIsolated yield after purification by
silica gel column chromatography .
Table S3: Control experiments for cycloaddition reactions between β-azido

glucose and 2-phenylethynea by using Sharpless and Fokin’s reagents.20
Entry CuSO4 sodium ascorbate CuSO4: sodium Time Conversion Yield

(mol%) (mol%) ascorbate ratio (h) (%)b (%)c
1 3 30 1:10 48 8 n.d.
2 20 40 1:2 20 7 n.d.
3 20 40 1:2 70 30 24d
4 20 100 1:5 20 15 n.d.
5 20 100 1:5 70 45 40
a
Reaction details: β-azido glucose (0.25 mmol, 1 equiv), 2-phenylethyne (0.375 mmol, 1.5
equiv) in t-BuOH:H2O (2 mL:1 mL). bConversion of β-azido glucose 1 was determined by 1H
NMR analysis of the crude reaction mixture. cIsolated yield after purification by silica gel
column chromatography. n.d. = not determined. dRemaining starting material was recovered.
S20
Table S4: Control experiments for cyclo-addition reaction between β-azido

glucose and 2-phenylethynea by using bimetallic catalyst Cu(OTf)2:Cu system.21
OAc OAc
Cu(OTf)2: Cu Powder N N
AcO O N3 AcO O
AcO N
Solvent AcO
OAc OAc
ambient temperature
1 (0.25 mmol) 1.5 equiv 12
Entry Cu(OTf)2 Cu Powder Cu(OTf)2: Solvent Time Conv. Yield

(mol%) (mol%) Cu(0) ratio (h) (%)b (%)c
1 10 10 1:1 CH3CN 40 21 16 d
2 10 50 1:5 CH3CN 12 quant. 92
3 10 10 1:1 t-BuOH:H2O 35 0 n.d.
4 10 50 1:5 t-BuOH:H2O 35 9 n.d.
a
Reaction details: β-azido glucose (0.25 mmol, 1 equiv), 2-phenylethyne (0.375 mmol, 1.5
equiv) in CH3CN (6 mL) or t-BuOH:H2O (2 mL:1 mL). bConversion of β-azido glucose 1 was
determined by 1H NMR analysis of the crude reaction mixture. cIsolated yield after purification
by silica gel column chromatography. n.d. = not determined. dRemaining starting material was
recovered.
(B) Detailed procedures for FeCl3:Cu catalyzed 1,3-dipolar cycloaddition and

analytical data for glycosyl 1,2,3-triazole conjugates 11-16.
Phenyl 2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-glucopyranosyl 1,2,3-triazole (11).22
In a 10 mL, round bottomed flask were placed 20 mol% of FeCl3 (8.1 mg, 0.05 mmol,
0.2 equiv) and Cu(s) powder (16 mg, 0.25 mmol, 1.0 equiv) in 1:1 mixture of
t-BuOH:H2O (1 mL : 1 mL). The resulting mixture was stirred at ambient temperature
for 5 min and a solution of 2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-gluco-pyranosyl azide

S21
1 (93 mg, 0.25 mmol, 1 equiv) in t-BuOH (1 mL) was added followed by addition of
ethynylbenzene (41 μL, 38 mg, 0.375 mmol, 1.5 equiv). The resulting reaction
organic volatiles were removed under reduced pressure and the resulting mixture was
partitioned between H2O and CH2Cl2 (5 mL each). The organic layer was separated
and the aqueous layer was extracted with CH2Cl2 (2 × 3 mL). The combined organic
layers were washed with brine (10 mL), dried (MgSO4), filtered, passed through
Celite bed to remove inorganic salts and concentrated under reduced pressure. The
resulting crude residue was purified by column chromatography (EtOAc/hexanes, 1/1)
on silica gel to afford 109 mg (92%) of phenyl 2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-
glucopyranosyl 1,2,3-triazole 11 as a white solid. 1H NMR (400 MHz, CDCl3) δ 8.0 (s,
1H), 7.83 (d, J = 7.2, 2H), 7.43 (t, J = 7.2, 2H,), 7.36 (d, J = 7.6, 1H), 5.93 (d, J = 9.2,
1H), 5.52 (t, J = 9.4, 1H), 5.44 (t, J = 9.4, 1H), 5.27 (t, J = 9.6, 1H), 4.33 (dd, J = 12.6,
5.0, 1H), 4.16 (dd, J = 12.6, 1.8, 1H), 4.05-4.02 (m, 1H), 2.084 (s, 3H, COCH3), 2.08
13
(s, 3H, COCH3), 2.04 (s, 3H, COCH3), 1.88 (s, 3H, COCH3); C NMR (100 MHz,
CDCl3) δ 170.5, 169.9, 169.4, 169.0, 148.5, 129.9, 128.9, 128.6, 125.9, 117.7, 85.8,
75.3, 72.7, 70.2, 67.7, 61.6, 20.7, 20.6, 20.5, 20.2; MS ESI (C22H25O9N3, 475): 498
(M+Na+, 100); TLC Rf 0.42 (EtOAc/hexanes, 1/1); m.p. 211-213 °C (lit.22b m.p.
S22
213-215 °C); [α]25D -54.5 (c 1.0, CHCl3) (lit.22c [α]20D -56.2 (c 1.0, CHCl3)).
Phenyl 3,4,6-tri-O-acetyl-2-N-acetyl-6-deoxy-β-D-glucopyranosyl 1,2,3-triazole

(12).
OAc OAc
N N
AcO O FeCl3:Cu powder (1:5) AcO O
N3 N
AcO t-BuOH:H2O (2:1) AcO
NHAc rt, 12 h NHAc
10 12
for 5 min and a solution of 3,4,6-tri-O-acetyl-2-N-acetyl-2-deoxy-β-D-glucopyranosyl
azide 10 (93 mg, 0.25 mmol, 1 equiv) in t-BuOH (1 mL) was added followed by
addition of ethynylbenzene (41 μL, 38 mg, 0.375 mmol, 1.5 equiv). The resulting

S23
on silica gel to afford 105 mg (89%) of phenyl 3,4,6-tri-O-acetyl-2-N-acetyl-6-deoxy-
β-D-glucopyranosyl 1,2,3-triazole 13 as a off white solid. 1H NMR (400 MHz,
CDCl3/CD3OD) δ 8.04 (s, 1H), 7.52 (d, J = 7.3, 2H), 7.13 (t, J = 7.4, 2H), 7.05 (d, J =
7.2, 1H), 5.81 (d, J = 10, 1H), 5.19 (t, J = 10, 1H), 4.99 (t, J = 9.6, 1H), 4.36 (t, J =
10.2, 1H), 4.05 (dd, J = 12.4, 4.8, 1H), 3.89-3.82 (m, 2H), 1.79 (s, 3H), 1.787 (s, 3H,
13
COCH3), 1.76 (s, 3H, COCH3), 1.46 (s, 3H, COCH3); C NMR (100 MHz,
CDCl3/CD3OD) δ 171.5, 170.6, 170.1, 169.4, 147.6, 129.2, 128.3, 128.0, 125.2, 118.7,
85.4, 74.2, 72.0, 67.8, 61.4, 52.6, 21.4, 19.7, 19.7, 19.6; MS ESI (C22H26O8N4, 474):
497 (M+Na+, 100); TLC Rf 0.40 (EtOAc/hexanes, 1/1); m.p. 228-229 °C; [α]25D -62.4
(c 1.0, CHCl3).
Phenyl 2,3,6-tri-O-acetyl-4-O-( 2’,3’,4’,6’-tetra-O-acetyl-β-D-glucopyranosyl)-β-

D-glucopyranosyl 1,2,3-triazole (13).22
In a 10 mL, round bottomed flask were placed 20 mol% of FeCl3 (8.1 mg, 0.05
mmol, 0.2 equiv) and Cu(s) powder (16 mg, 0.25 mmol, 1.0 equiv) in 1:1 mixture of
t-BuOH:H2O (1 mL : 1 mL). The resulting mixture was stirred at ambient
temperature for 5 min and a solution of 2,3,6-tri-O-acetyl-4-O-(2’,3’,4’,6’-tetra-O-
acetyl-β-D-glucopyranosyl)-β-D-glucopyranosylazide 7 (165 mg, 0.25 mmol, 1 equiv)

S24
in t-BuOH (1 mL) was added followed by addition of ethynylbenzene (41 μL, 38 mg,
0.375 mmol, 1.5 equiv). The resulting reaction mixture was stirred at ambient
temperature and the progress of the reaction was monitored by TLC. After complete
consumption of starting material in 12 h, the organic volatiles were removed under
reduced pressure and the resulting mixture was partitioned between H2O and CH2Cl2
(5 mL each). The organic layer was separated and the aqueous layer was extracted
with CH2Cl2 (2 × 3 mL). The combined organic layers were washed with brine (10
mL), dried (MgSO4), filtered, passed through Celite bed to remove inorganic salts
and concentrated under reduced pressure. The resulting crude residue was purified
by column chromatography (EtOAc/hexanes, 3/2) on silica gel to afford 166 mg
(87%) of phenyl 2,3,6-tri-O-acetyl-4-O-( 2’,3’,4’,6’-tetra-O-acetyl-β-D-glucopyran-
osyl)-β-D-glucopyranosyl 1,2,3-triazole 13 as a off white solid. 1H NMR (400 MHz,
CDCl3) δ 7.92 (s, 1H), 7.81 (d, J = 7.6, 2H), 7.42 (t, J = 7.4, 2H), 7.34 (d, J = 7.4,
1H), 5.94 (d, J = 9.2, 1H), 5.51-5.36 (m, 4H), 5.07 (t, J = 9.8, 1H), 4.88 (dd, J = 10.8,
4, 1H), 4.49 (dd, J = 12.4, 2.0, 1H), 4.29-4.23 (m, 2H), 4.17 (t, J = 8.8, 1H), 4.08 (dd,
J = 12.6, 1.8, 1H), 4.02-3.99 (m, 2H), 2.12 (s, 3H, COCH3), 2.10 (s, 3H, COCH3),
2.07 (s, 3H, COCH3), 2.03 (s, 3H, COCH3), 2.01 (s, 3H, COCH3), 1.85 (s, 3H,
COCH3); 1.72 (s, 3H, COCH3); 13C NMR (100 MHz, CDCl3) δ 170.5, 170.5, 170.3,
169.9, 169.4, 169.3, 148.4, 129.9, 128.9, 128.6, 125.9, 95.9, 85.3, 75.4, 75.2, 72.5,
S25
70.8, 70.0, 69.2, 68.8, 67.9, 62.5, 61.5, 20.8, 20.7, 20.6, 20.6, 20.2; MS ESI
(C34H41O17N3, 763): 786 (M+Na+, 100); TLC Rf 0.21 (EtOAc/hexanes, 1/1); m.p.
170-171 °C; [α]25D -38.5 (c 1.0, CHCl3).
Phenyl 2,3,5-tri-O-acetyl-β-D-ribofuranosyl 1,2,3-triazole (14).22
for 5 min and a solution of 2,3,5-tri-O-acetyl-β-D-ribofurunosyl azide 4 (75 mg, 0.25
mmol, 1 equiv) in t-BuOH (1 mL) was added followed by addition of ethynylbenzene
(41 μL, 38 mg, 0.375 mmol, 1.5 equiv). The resulting reaction mixture was stirred at
complete consumption of starting material in 8 h, the organic volatiles were removed
under reduced pressure and the resulting mixture was partitioned between H2O and
CH2Cl2 (5 mL each). The organic layer was separated and the aqueous layer was
extracted with CH2Cl2 (2 × 3 mL). The combined organic layers were washed with
brine (10 mL), dried (MgSO4), filtered, passed through Celite bed to remove
S26
inorganic salts and concentrated under reduced pressure. The resulting crude residue
was purified by column chromatography (EtOAc/hexanes, 1/1) on silica gel to afford
97 mg (96%) of phenyl 2,3,5-tri-O-acetyl-β-D-ribofuranosyl 1,2,3-triazole 14 as a
colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.96 (s, 1H), 7.80 (d, J = 7.2, 2H), 7.40 ( t,
J = 7.6, 2H), 7.32 (d, J = 7.2, 1H), 6.18 (d, J = 3.6, 1H), 5.9 (dd, J = 4.8, 4.0, 1H),
5.63 (t, J = 5.4, 1H), 4.48 (dd, 8.2, 4.2, 1H), 4.40 (dd, J = 12.4, 2.8, 1H), 4.23 (dd, J =
13
12.4, 4, 1H), 2.10 (s, 6H, 2 × COCH3), 2.02 (s, 3H, COCH3); C NMR (100 MHz,
CDCl3) δ 170.2, 169.3, 169.2, 148.0, 129.9, 128.8, 125.7, 118.8, 89.9, 80.0, 74.1, 70.6,
62.7, 20.5, 20.3, 20.2; MS ESI (C19H21O7N3, 403): 426 (M+Na+, 100); TLC Rf 0.43
(EtOAc/hexanes, 1/1); [α]25D +87.2 (c 1.0, CHCl3).
2,3,4,6-tetra-O-acetyl-(4’-ethylcarboxylate)-β-D-glucopyranosyl 1,2,3-triazole
(15).22
In a 10 mL, round bottomed flask, 20 mol% of FeCl3 (8.1 mg, 0.05 mmol, 0.2 equiv)
and Cu(s) powder (16 mg, 0.25 mmol, 1.0 equiv) were placed in 1:1 mixture of
S27
ethyl propiolate (38 μL, 37 mg, 0.375 mmol, 1.5 equiv). The resulting reaction
on silica gel to afford 112 mg (95%) of 2,3,4,6-tetra-O-acetyl-(4’-ethyl
carboxylate)-β-D-glucopyranosyl 1,2,3-triazole 15 as a white solid. 1H NMR (400
MHz, CDCl3) δ 8.33 (s, 1H), 5.92 (d, J = 8.8, 1H), 5.46-5.37 (m, 2H), 5.24 (t, J = 9.6,
1H), 4.42 (q, J = 7.1, 2H), 4.31 (dd, J = 12.6, 5.0, 1H), 4.15 (dd, J = 12.8, 1.4, 1H),
4.03-4.0 (m, 1H), 2.08 (s, 3H, COCH3), 2.06 (s, 3H, COCH3), 2.02 (s, 3H, COCH3),
1.89 (s, 3H, COCH3), 1.41 (t, J = 7, 3H); 13C NMR (100 MHz, CDCl3) δ 170.4, 169.8,
169.3, 168.8, 160.1, 140.9, 126.0, 85.8, 75.3, 72.3, 70.4, 67.5, 61.5, 61.4, 20.6, 20.4,
20.0, 14.2; MS ESI (C19H25O11N3, 494): 517 (M+Na+, 100); TLC Rf 0.39
(EtOAc/hexanes, 1/1); m.p. 170-171 °C (lit.22d m.p. 172-174 °C); [α]25D -46.3 (c 1.0,
CHCl3) (lit.22d [α]25D -62 (c 0.2, CHCl3)).

S28
2,3,4,6-tetra-O-acetyl-(4’-hydroxymethyl)-6-deoxy-β-D-glucopyranosyl
1,2,3-triazole (16).22
prop-2-yn-1-ol (22 μL, 21 mg, 0.375 mmol, 1.5 equiv). The resulting reaction mixture
was stirred at ambient temperature and the progress of the reaction was monitored by
TLC. After complete consumption of starting material in 12 h, the organic volatiles
were removed under reduced pressure and the resulting mixture was partitioned
between H2O and CH2Cl2 (5 mL each). The organic layer was separated and the
aqueous layer was extracted with CH2Cl2 (2 × 3 mL). The combined organic layers
were washed with brine (10 mL), dried (MgSO4), filtered, passed through Celite bed
to remove inorganic salts and concentrated under reduced pressure. The resulting
crude residue was purified by column chromatography (EtOAc/hexanes, 1/1) on silica

S29
gel to afford 100 mg (93%) of 2,3,4,6-tetra-O-acetyl-(4’-hydroxymethyl) -6-deoxy-β-
1
D-glucopyranosyl 1,2,3-triazole 16 as a off white solid. H NMR (400 MHz, CDCl3) δ
7.84 (s, 1H), 5.89 (d, J = 8.4, 1H), 5.46-5.37 (m, 2H), 5.23 (t, J = 9.4, 1H), 4.74 (brs,
2H), 4.25 (dd, J = 12.6, 5, 1H), 4.10 (d, J = 12.4, 1H), 4.01-3.99 (m, 1H), 3.42 (brs,
1H), 2.021 (s, 3H, COCH3), 2.02 (s, 3H, COCH3), 1.98 (s, 3H, COCH3), 1.82 (s, 3H,
13
COCH3); C NMR (100 MHz, CDCl3) δ 170.5, 169.9, 169.4, 169.0, 148.5, 120.2,
85.6, 75.0, 72.6, 70.3, 67.7, 61.5, 56.3, 20.6, 20.5, 20.4, 20.1; MS ESI (C17H23O10N3,
429): 452 (M+Na+, 100); TLC Rf 0.40 (EtOAc/hexanes, 1/1); m.p. 149-151 °C (lit.22d
m.p. 152-154 °C); [α]25D -9.1 (c 1.0, CHCl3) (lit.22c [α]20D -6 (c 1.0, CHCl3)).
(C) Procedure for one pot synthesis of 2,3,4,6-tetra-O-acetyl-4’-O-(2,3,4,6-tetra

-O- acetyl-6-deoxy-glucopyranose)-6-deoxy-β-D-glucopyranosyl triazole (17).22
OAc
AcO O
O
AcO
OAc 1.5 equiv TMSN3, OAc OAc OAc AcO
AcO O 5 mol% FeCl3 AcO O FeCl3:Cu powder AcO N N OAc
OAc N3 O O
AcO AcO (1:5) AcO N O OAc
OAc CH2Cl2 (1 mL) OAc
rt, 6h t-BuOH:H2O (2:1) OAc AcO
1 rt, 12 h 17
(2S,3S,4S,5R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (98
mg, 0.25 mmol, 1 equiv) in CH2Cl2 (0.25 mL) was added. After having been stirred
for 5 min, a solution of TMSN3 (50 μL, 44 mg, 0.38 mmol, 1.5 equiv) in CH2Cl2
(0.25 mL) was added slowly. The resulting reaction mixture was stirred at ambient
S30
temperature and the progress of the reaction was monitored by TLC. After complete
consumption of starting material in 6 h as judged by TLC, the reaction mixture was
concentrated under reduced pressure and the resulting residue was dried in vacuo. The
residue was then suspended in a mixture of t-BuOH:H2O (1 mL: 1 mL). After having
been stirred for 5 min, a solution of 15 mol% of FeCl3 (6.0 mg, 0.0375 mmol, 0.15
equiv) and (3R,4S,5S,6R)-2-(acetoxymethyl)-6-(prop-2-ynyloxy)tetrahydro-2H-pyran
-3,4,5-triyl triacetate (145 mg, 0.375 mmol, 1.5 equiv) in t-BuOH (1 mL) was added
followed by addition of Cu(s) powder (16 mg, 0.25 mmol, 1.0 equiv). After having
been stirred for 12 h at ambient temperature, the organic volatiles were removed
under reduced pressure and the resulting mixture was partitioned between H2O and
CH2Cl2 (5 mL each). The organic layer was separated and the aqueous layer was
extracted with CH2Cl2 (2 × 3 mL). The combined organic layers were washed with
brine (10 mL), dried (MgSO4), filtered and passed through Celite bed to remove
inorganic salts. The organic layer was then concentrated under reduced pressure and
the resulting crude residue was purified by column chromatography (EtOAc/hexanes,
1/1) on silica gel to afford 171 mg (90%) of 17 as a white solid. 1H NMR (400 MHz,
CDCl3) δ 7.80 (s, 1H), 5.86 (d, J = 8.8, 1H), 5.42-5.39 (m, 2H), 5.23 (t, J = 9.6, 1H),
5.16 (t, J = 9.4, 1H), 5.08 (t, J = 9.6, 1H), 4.97 (td, J = 8.2, 1.2, 1H), 4.90 (d, J = 12.8,
1H), 4.79 (d, J = 12.8, 1H), 4.53 (d, J = 8.0, 1H), 4.31-4.25 (m, 2H), 4.19-4.10 (m,
S31
1H), 4.02-3.98 (m, 1H), 3.76-3.72 (m, 1H), 2.10 (s, 3H, COCH3), 2.06 (s, 3H,
13
CDCl3) δ 170.7, 170.4, 170.2, 169.8, 169.4, 169.3, 169.0, 144.2, 121.9, 98.7, 75.2,
72.6, 72.4, 71.7, 71.0, 70.4, 68.3, 67.6, 61.8, 61.7, 61.4, 20.7, 20.6, 20.5, 20.5, 20.0;
MS ESI (C30H39O19N3, 745): 768 (M+Na+, 100); TLC Rf 0.33 (EtOAc/hexanes, 1/1);
m.p. 198-200 °C (lit.23 m.p. 199-199.5 °C); [α]25D -41.6 (c 1.0, CHCl3).
References:
(1) H. Bretting, G. Jacobs, I. Benecke, W.A. Koenig and J. Thiem, Carbohydr. Res.,
1985, 139, 225.
(2) (a) G. Hodosi and P. Kovac,Carbohydr. Res., 1997, 303, 239; (b) J.-P. Utille and
D. Gagnaire, Carbohydr. Res., 1982, 106, 43.
(3) H. Ishii, I. Kitagawa, K. Matsushita, K. Shirakawa and K. Tori, Tetrahedron Lett.,
1981, 22, 1529.
(4) J. Xue, Y. Pan and Z. Guo, Tetrahedron Lett., 2002, 43, 1599.
(5) A. Yoshida, T. Hayashi, N. Takeda, S. Oida and E. Ohki, Chem. Pharm. Bull.,
1981, 29, 1854.
(6) N. Thiebault, D. Lesur, P. Gode, V. Moreau and F. Djedaini-Pilard, Carbohydr.
Res., 2008, 343, 2719.
(7) (a) C.O. Kappe, Angew. Chem. Int. Ed. Engl., 2004, 43, 6250; (b) D. D. Heard and
R. Barker, J. Org. Chem., 1968, 33, 740.
8 (a) For a discussion on the hazards associated with azides, see: Prudent Practice for
S32
Handling Hazardous Chemicals in Laboratories, National Academic Press,
Washington, DC, 1983, p. 87-88; (b) For human toxicity, see: The Merck Index, 12th
ed., Merck & Co., Rahway, NJ, 1996; p. 4818 and 8726.
9 (a) R. E. Conrow and W. D. Dean, Org. Process res. Dev., 2008, 12, 2285; (b) A. Hassner,
M. Stern and H. E. Gottlieb, J. Org. Chem., 1990, 55, 2304.
(10) F. D. Tropper, F. O. Andersson, S. Braun and R. Roy, Synthesis, 1992, 618.
(11) H. J. Berthold, S. Franke, J. Thiem and T. Schotten, J. Org.Chem., 2010, 75, 3859.
(12) H. Paulsen, Z. Gyorgydecik and M. Friedmann, Chem. Ber., 1974, 107, 1568.
(13) K.Slamova, P. Marhol, K. Bezouska, V. Kren, L. Lindkvist, S. G. Hansen and H. H.
Jensen, Bioorg. Med. Chem. Lett., 2010, 20, 4263.
(14) A. Stimac and J. Kobe, Carbohydr. Res., 1992, 232, 359.
(15) A. E. Meslouti, D. Beaupere, G. Demailly and R. Uzan, Tetrahedron Lett., 1994,
35, 3913.
(16) (a) X. Zheng, J. Morgan, S. K. Pandey, Y. Chen, E. Tracy, H. Baumann, J. R.
Missert, C. Batt, J. Jackson, D. A. Bellnier, B. W. Henderson, and R. K. Pandey, J.
Med. Chem., 2009, 52, 4306; (b) M. Tamura and H. Okai, Carbohydr. Res., 1984, 133,
207.
(17) (a) L. Marmuse, S. A. Nepogodiev and R. A. Field, Org. Biomol. Chem., 2005, 3,
2225; (b) S. A. Nepogodiev, S. Dedola, L. Marmuse, M. Y. Oliveira, and R. A.
Field, Carbohydr. Res., 2007, 342, 529.
(18) (a) A. Dan, M. Lergenmüller, M. Amano, Y. Nakahara, T. Ogawa and Y. Ito,
Chem. Eur. J., 1998, 4, 2182; (b) L. Szilagyi, and Z. Gyoergydeak, Carbohydr. Res.,
1985 , 143, 21.
(19) D. Macmillan, A. M. Daines, M. Bayrhuber and S. L. Flitsch, Org. Lett., 2002 , 4,
1467.
(20) (a) V. V. Rostovtsev, L. G. Green, V. V. Fokin and K. B. Sharpless, Angew. Chem.

S33
Int. Ed. Engl., 2002, 41, 2596; (b) S. Dedola, D. L. Hughes, S. A. Nepogodiev, M.
Rejzek and R. A. Field, Carbohydr. Res., 2010, 345, 1123.
(21) S. K. Yousuf, S. C. Taneja and D. Mukherjee, J. Org. Chem., 2010, 75, 3097.
(22) (a) R. Kumar, P. R. Maulik and A.K. Misra, Glycoconj. J., 2008, 25, 595; (b) L.
L. Rossi and A. Basu, Bioorg. Med. Chem. Lett., 2005, 15, 3596; (c) S. Dedola, S. A.
Nepogodiev, M. Rejzek, R. A. Field and D. L. Hughes, Carbohyd. Res., 2010, 345,
1123; (d) Bokor, E. Somsak, L. Docsa, T. and Gergely, P. Bioorg. Med. Chem., 2010,
18, 1171.
(23) V. O. Rodionov, S. I. Presolski, S. Gardinier, Y. H. Lim and M. G. Finn, J. Am.
Chem. Soc., 2007, 129, 12696.

S34
7.260
5.216
5.192
5.169
5.099
5.074
5.050
4.948
4.925
4.902
4.638
4.616
4.268
4.256
4.237
4.225
4.160
4.155
4.129
4.124
3.798
3.792
3.786
3.780
3.773
3.767
3.761
3.755
2.071
2.047
2.002
1.979
Current Data Parameters
NAME B-001-L
EXPNO 6
PROCNO 1
F2 - Acquisition Parameters
Date_ 20081204
OAc Time 23.32
INSTRUM spect
AcO O PROBHD 5 mm BBO BB-1H
N3 PULPROG zg30
AcO TD 16384
OAc SOLVENT CDCl3
1 NS 16
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
AQ 1.3664756 sec
5.216
5.192
5.169
5.099
5.074
5.050
4.948
4.925
4.902
4.638
4.616
4.268
4.256
4.237
4.225
4.160
4.155
4.129
4.124
3.798
3.792
3.786
3.780
3.773
3.767
3.761
3.755
RG 22
DW 83.400 usec
DE 6.50 usec
TE 299.9 K
D1 1.50000000 sec
MCREST 0.00000000 sec
MCWRK 0.01500000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 ppm PL1 0.00 dB
SFO1 400.1326008 MHz
F2 - Processing parameters
SI 16384
SF 400.1300091 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
1D NMR plot parameters
10 9 8 7 6 5 4 3 2 1 ppm CX 20.00 cm
CY 15.15 cm
F1P 2.087 ppm
1.048
1.046
1.087
1.043
1.058
1.073
1.032
3.000
3.012
3.009
3.025
F1 834.90 Hz
S35
170.49
170.01
169.22
169.11
NAME B-001-L
87.81
77.32
77.00
76.68
73.95
72.53
70.58
67.83
61.59
20.59
20.44
EXPNO 7
PROCNO 1
Date_ 20081204
Time 23.37
INSTRUM spect
OAc PROBHD 5 mm BBO BB-1H
PULPROG zgpg30
AcO O N3 TD 65536
SOLVENT CDCl3
AcO NS 29
OAc DS 0
1 SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 4096
DW 19.900 usec
DE 6.50 usec
TE 299.7 K
D1 1.50000000 sec
d11 0.03000000 sec
DELTA 1.39999998 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127672 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S36
7.259
5.415
5.409
5.291
5.176
5.154
5.151
5.129
5.044
5.035
5.018
5.009
4.602
4.580
4.183
4.172
4.162
4.155
4.147
4.024
4.022
4.006
3.991
3.990
2.161
2.082
2.053
1.980
NAME galactose azide-pure
EXPNO 1
PROCNO 1
Date_ 20090405
OAc OAc Time 19.50
INSTRUM spect
O PROBHD 5 mm BBO BB-1H
AcO N3
PULPROG zg30
OAc TD 16384
2 SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
AQ 1.3664756 sec
RG 128
5.176
5.154
5.151
5.129
5.044
5.035
5.018
5.009
4.602
4.580
4.183
4.172
4.162
4.155
4.147
4.024
4.022
4.006
3.991
3.990
DW 83.400 usec
DE 6.50 usec
TE 298.0 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
5.2 5.1 5.0 4.9 4.8 4.7 ppm 4.2 4.1 4.0 ppm
PL1 0.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1300095 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm CX 20.00 cm
CY 10.50 cm
F1P 2.240 ppm
1.052
1.007
1.002
1.004
2.021
1.029
3.002
3.082
3.057
3.008
F1 896.10 Hz
S37
OAc OAc
O
AcO N3
OAc
2
S38
AcO OAc
AcO O
AcO
3 N3
S39
AcO OAc
AcO O
AcO
3 N3
S40
7.259
5.336
5.332
5.314
5.301
5.297
5.285
5.112
5.108
5.100
5.096
4.399
4.391
4.369
4.361
4.339
4.329
4.322
4.313
4.304
4.139
4.128
4.108
4.098
2.092
2.089
2.040
NAME ribose-azide
EXPNO 1
PROCNO 1
Date_ 20090121
Time 13.56
O N3 INSTRUM spect
AcO PROBHD 5 mm BBO BB-1H
PULPROG zg30
TD 16384
AcO OAc SOLVENT CDCl3
4 NS 1
DS 0
SWH 5995.204 Hz
4.399
4.391
4.369
4.361
4.339
4.329
4.322
4.313
4.304
4.139
4.128
4.108
4.098
FIDRES 0.365918 Hz
5.336
5.332
5.314
5.301
5.297
5.285
5.112
5.108
5.100
5.096
AQ 1.3664756 sec
RG 57
DW 83.400 usec
DE 6.50 usec
TE 297.8 K
D1 1.50000000 sec
======== CHANNEL f1 ========

5.3 5.2 5.1 ppm NUC1 1H
4.4 4.3 4.2 ppm
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1300088 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00

10 9 8 7 6 5 4 3 2 1 ppm CX 20.00 cm
CY 21.22 cm
F1P 2.133 ppm
1.021
1.012
1.000
1.005
1.018
1.002
6.045
3.009
F1 853.54 Hz
S41
170.47
169.45
169.31
NAME ribose-azide
92.56
79.28
77.32
77.00
76.68
74.37
70.37
62.91
20.56
20.39
20.34
EXPNO 2
PROCNO 1
Date_ 20090121
Time 14.00
INSTRUM spect
PROBHD 5 mm BBO BB-1H
PULPROG zgpg30
TD 65536
O N3 SOLVENT CDCl3
NS 62
AcO DS 0
SWH 25125.629 Hz
AcO OAc FIDRES 0.383387 Hz
4 AQ 1.3042164 sec
RG 4096
DW 19.900 usec
DE 6.50 usec
TE 297.8 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127535 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S42
7.259
5.204
5.182
5.160
5.007
4.994
4.984
4.971
4.961
4.948
4.891
4.871
4.849
4.639
4.619
4.230
4.216
4.200
4.187
3.459
3.436
3.430
3.406
2.074
2.042
2.036
NAME xylose azide
EXPNO 1
PROCNO 1
Date_ 20081212
AcO O Time 20.32
N3 INSTRUM spect
AcO PROBHD 5 mm BBO BB-1H
OAc PULPROG zg30
5 TD 16384
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
4.230
4.216
4.200
4.187
3.459
3.436
3.430
3.406
5.204
5.182
5.160
5.007
4.994
4.984
4.971
4.961
4.948
4.891
4.871
4.849
4.639
4.619
FIDRES 0.365918 Hz
AQ 1.3664756 sec
RG 203.2
DW 83.400 usec
DE 6.50 usec
TE 298.9 K
D1 1.50000000 sec
======== CHANNEL f1 ========

5.2 5.1 5.0 4.9 4.8 4.7 ppm 4.2 4.0 3.8 3.6 ppm
NUC1 1H
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1300091 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm 1D NMR plot parameters

CX 20.00 cm
CY 10.50 cm
1.000
1.052
1.014
1.015
1.037
1.093
3.096
6.083
F1P 5.373 ppm
F1 2150.09 Hz
S43
169.94
169.68
169.25
NAME nsp-triazole-clcl
88.32
77.32
77.00
76.68
71.54
70.43
68.43
64.28
20.61
20.55
EXPNO 2
PROCNO 1
Date_ 20081227
Time 22.21
INSTRUM spect
PULPROG zgpg30
O TD 65536
AcO N3 SOLVENT CDCl3
AcO NS 182
OAc DS 0
5 SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 4096
DW 19.900 usec
DE 6.50 usec
TE 302.9 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127466 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S44
7.260
5.343
5.334
5.220
5.197
5.173
5.115
5.095
5.089
5.069
4.963
4.954
4.937
4.928
4.870
4.848
4.824
4.630
4.608
4.515
4.510
4.484
4.464
4.140
4.130
4.124
4.118
4.112
4.096
4.090
4.073
4.045
3.883
3.865
3.849
3.831
3.806
3.783
3.714
3.709
3.701
3.697
3.684
2.140
2.126
2.061
2.053
2.037
1.953
NAME Lact azide-pure
EXPNO 1
PROCNO 1
Date_ 20100428
5.343
5.334
5.220
5.197
5.173
5.115
5.095
5.089
5.069
4.963
4.954
4.937
4.928
4.870
4.848
4.824
OAc OAc Time 15.46
INSTRUM spect
O OAc PROBHD 5 mm BBO BB-1H
O PULPROG zg30
AcO O
N3 TD 16384
OAc AcO SOLVENT CDCl3
OAc NS 16
6 DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
5.3 5.2 5.1 5.0 4.9 ppm AQ 1.3664756 sec
RG 114
DW 83.400 usec
4.630
4.608
4.515
4.510
4.484
4.464
4.140
4.130
4.124
4.118
4.112
4.096
4.090
4.073
4.063
4.045
3.883
3.865
3.849
3.831
3.806
3.783
3.714
3.709
3.701
3.697
3.689
3.684
3.677
3.672
DE 8.00 usec
TE 673.2 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 ppm
SI 16384
SF 400.1300091 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00

CX 20.00 cm
CY 11.96 cm
1.050
1.011
1.010
1.017
1.024
1.017
2.003
3.096
1.024
0.996
0.999
3.088
3.063
3.028
3.005
6.076
3.000 F1P 2.194 ppm
F1 877.95 Hz
S45
170.31
170.08
170.01
169.60
169.45
169.05
101.07
NAME Lact azide-pure
87.67
77.32
77.00
76.69
75.74
74.77
72.50
70.96
70.90
70.73
69.04
66.56
61.70
60.76
20.75
20.68
20.58
20.45
EXPNO 2
PROCNO 1
Date_ 20100428
Time 15.47
INSTRUM spect
PULPROG zgpg30
OAc OAc TD 65536
SOLVENT CDCl3
O OAc NS 97
O
AcO O DS 0
OAc AcO N3 SWH 25125.629 Hz
FIDRES 0.383387 Hz
OAc AQ 1.3042164 sec
6 RG 8192
DW 19.900 usec
DE 8.00 usec
TE 673.2 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6243390 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127690 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S46
7.260
5.410
5.400
5.373
5.349
5.323
5.279
5.256
5.234
5.074
5.050
5.025
4.872
4.862
4.845
4.835
4.803
4.782
4.759
4.714
4.692
4.524
4.518
4.494
4.487
4.263
4.259
4.254
4.248
4.232
4.222
4.218
4.065
4.059
4.035
4.028
4.012
3.989
3.962
3.937
3.793
3.789
2.152
2.099
2.047
2.037
2.022
2.008
1.998
NAME Maltose azide-pure
EXPNO 1
PROCNO 1
5.410
5.400
5.373
5.349
5.323
5.295
5.279
5.256
5.234
5.074
5.050
5.025
4.872
4.862
4.845
4.835
4.803
4.782
4.759
4.714
4.692
Date_ 20100331
Time 16.24
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
5.4 5.3 5.2 5.1 5.0 4.9 4.8 ppm FIDRES 0.365918 Hz
AQ 1.3664756 sec
4.524
4.518
4.494
4.487
4.263
4.259
4.254
4.248
4.232
4.222
4.218
4.065
4.059
4.035
4.028
4.012
3.989
3.968
3.962
3.954
3.943
3.937
3.928
3.800
3.793
3.789
3.782
3.776
3.769
3.765
3.758
RG 322.5
DW 83.400 usec
DE 6.50 usec
TE 297.8 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 9.70 usec
4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 ppm PL1 3.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1300095 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00

CX 20.00 cm
CY 10.42 cm
1.042
1.071
1.111
1.099
1.067
1.036
1.008
1.073
1.076
1.033
2.056
1.034
1.036
3.050
3.061
3.078
3.042
3.001
3.000
3.052 F1P 5.482 ppm
F1 2193.37 Hz
S47
170.35
170.25
169.94
169.77
169.33
169.26
NAME pure
95.58
87.28
77.33
77.01
76.69
74.91
74.12
72.33
71.35
69.87
69.13
68.49
67.87
62.42
61.37
20.67
20.58
20.49
20.39
EXPNO 2
PROCNO 1
Date_ 20100410
Time 15.39
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 93
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 181
DW 19.900 usec
DE 8.00 usec
TE 673.2 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6243390 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 100.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127533 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S48
5.372
5.361
5.354
5.350
5.342
5.329
5.317
5.292
5.276
5.252
5.238
5.229
5.208
5.029
4.835
4.825
4.809
4.799
4.741
4.722
4.719
4.713
4.693
4.687
4.671
4.456
4.449
4.441
4.415
4.410
4.301
4.199
4.190
4.039
4.034
3.949
3.933
3.926
3.916
3.894
2.147
2.119
2.061
2.016
2.013
1.995
1.982
1.968
1.962
NAME PTHALIC-12PH-INDOL
EXPNO 6
PROCNO 1
Date_ 20090321
Time 21.25
5.372
5.361
5.354
5.350
5.342
5.329
5.317
5.292
5.276
5.252
5.238
5.229
5.208
5.054
5.029
5.005
4.835
4.825
4.809
4.799
4.763
4.741
4.722
4.719
4.713
4.693
4.687
4.671
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT CDCl3
NS 32
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 ppm AQ 1.3664756 sec
RG 40.3
DW 83.400 usec
DE 6.50 usec
TE 299.9 K
D1 1.50000000 sec
4.487
4.481
4.456
4.449
4.441
4.415
4.410
4.311
4.301
4.281
4.270
4.230
4.221
4.199
4.190
4.168
4.160
4.137
4.129
4.108
4.090
4.073
4.055
4.039
4.034
4.008
4.003
3.972
3.949
3.933
3.926
3.916
3.894
3.870
3.808
3.799
3.791
3.785
3.777
3.768
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 ppm SI 16384
SF 400.1300091 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
CX 20.00 cm
10 9 8 7 6 5 4 3 2 1 ppm CY 10.50 cm
F1P 2.281 ppm
F1 912.69 Hz
2.030
1.057
2.033
1.048
1.022
3.066
2.023
1.012
1.062
1.007
1.030
1.124
3.056
1.028
3.054
3.029
3.012
6.200
3.016
3.090
9.008
S49
170.46
170.40
170.32
170.22
169.87
169.72
169.59
169.39
169.32
NAME maltose azide
95.81
95.57
87.29
77.32
77.00
76.68
74.81
74.08
73.41
72.44
71.55
71.42
70.32
69.98
69.24
68.97
68.42
67.81
62.59
62.21
61.29
20.77
20.68
20.54
20.45
20.42
EXPNO 2
PROCNO 1
Date_ 20090323
Time 19.35
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 75
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 8192
DW 19.900 usec
DE 6.50 usec
TE 298.5 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127528 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S50
OAc
AcO O
N3
AcO
O N O
9
S51
OAc
AcO O
N3
AcO
O N O
9
S52
7.263
6.098
6.076
5.279
5.254
5.229
5.104
5.080
5.056
4.792
4.769
4.276
4.264
4.245
4.233
4.164
4.138
4.133
3.952
3.928
3.903
3.880
3.821
3.815
3.809
3.802
3.796
3.790
2.085
2.024
2.016
1.965
1.232
NAME NH AC azide C13
EXPNO 1
PROCNO 1
Date_ 20091218
Time 21.49
INSTRUM spect
PULPROG zg30
OAc TD 16384
SOLVENT CDCl3
AcO O N3 NS 1
AcO DS 0
SWH 5995.204 Hz
NHAc FIDRES 0.365918 Hz
10 AQ 1.3664756 sec
RG 90.5
4.276
4.264
4.245
4.233
4.164
4.138
4.133
3.952
3.928
3.903
3.880
3.821
3.815
3.809
3.802
3.796
3.790
DW 83.400 usec
6.098
6.076
5.279
5.254
5.229
5.104
5.080
5.056
4.792
4.769
DE 6.50 usec
TE 297.2 K
D1 1.50000000 sec
======== CHANNEL f1 ========
NUC1 1H
P1 10.00 usec
PL1 0.00 dB
4.3 4.2 4.1 4.0 3.9 3.8 ppm SFO1 400.1326008 MHz
6.0 5.8 5.6 5.4 5.2 5.0 ppm SI 16384
SF 400.1300074 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm
1.000
1.080
1.060
1.001
1.139
1.081
1.046
1.063
3.116
6.366
3.165
S53
170.90
170.67
170.58
169.27
NAME NH AC azide C13
88.33
77.32
77.21
77.00
76.68
73.86
72.12
68.11
61.85
54.01
23.13
20.66
20.57
20.52
EXPNO 2
PROCNO 1
Date_ 20091218
Time 21.50
INSTRUM spect
OAc PULPROG zgpg30
TD 65536
O SOLVENT CDCl3
AcO N3 NS 98
AcO DS 0
NHAc SWH 25062.656 Hz
10 FIDRES 0.382426 Hz
AQ 1.3074932 sec
RG 8192
DW 19.950 usec
DE 6.50 usec
TE 297.2 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6243390 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 100.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127513 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S54
8.004
7.842
7.824
7.448
7.430
7.411
7.368
7.349
7.331
7.260
5.946
5.923
5.548
5.524
5.501
5.465
5.441
5.418
5.294
5.270
5.246
4.350
4.337
4.318
4.306
4.176
4.171
4.144
4.140
4.054
4.049
4.042
4.037
4.029
4.024
4.016
4.011
2.084
2.075
2.036
1.881
1.659
NAME glucose triazole pur
EXPNO 1
PROCNO 1
5.946
5.923
5.548
5.524
5.501
5.465
5.441
5.418
5.294
5.270
5.246
Date_ 20090411
Time 20.58
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
5.9 5.8 5.7 5.6 5.5 5.4 5.3 ppm FIDRES 0.365918 Hz
AQ 1.3664756 sec
7.842
7.824
7.448
7.430
7.411
7.368
7.349
7.331
RG 161.3
DW 83.400 usec
DE 6.50 usec
4.350
4.337
4.318
4.306
4.176
4.171
4.144
4.140
4.054
4.049
4.042
4.037
4.029
4.024
4.016
4.011
TE 297.6 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
7.8 7.7 7.6 7.5 7.4 ppm P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
4.3 4.2 4.1 4.0 ppm
SI 16384
SF 400.1300095 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00

CX 20.00 cm
CY 10.50 cm
1.000
2.008
2.006
1.026
1.014
1.012
1.012
1.041
1.036
1.056
1.024
3.092
3.075
3.027
3.011
F1P 2.155 ppm
F1 862.43 Hz
S55
170.46
169.88
169.35
168.98
148.48
129.87
128.85
128.55
125.89
117.69
NAME dr-12
85.79
77.32
77.00
76.68
75.16
72.72
70.19
67.74
61.56
20.65
20.51
20.14
EXPNO 9
PROCNO 1
Date_ 20090307
Time 21.22
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 151
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 4096
DW 19.900 usec
DE 6.50 usec
TE 299.0 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127672 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S56
8.035
7.528
7.509
7.260
7.150
7.132
7.113
7.072
7.054
7.036
5.822
5.797
5.215
5.190
5.165
4.997
4.973
4.949
4.390
4.365
4.339
4.263
4.073
4.061
4.042
4.030
3.896
3.864
3.846
3.831
3.827
3.821
1.788
1.787
1.763
1.455
NAME NHac
EXPNO 1
PROCNO 1
Date_ 20090405
4.390
4.365
4.339
4.263
4.073
4.061
4.042
4.030
3.896
3.864
3.846
3.831
3.827
3.821
Time 17.49
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT MeOD
NS 16
DS 0
SWH 5995.204 Hz
4.4 4.2 4.0 3.8 ppm FIDRES 0.365918 Hz
AQ 1.3664756 sec
RG 57
7.528
7.509
7.260
7.150
7.132
7.113
7.072
7.054
7.036
5.822
5.797
5.215
5.190
5.165
4.997
4.973
4.949
DW 83.400 usec
DE 6.50 usec
TE 298.0 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
5.8 5.6 5.4 5.2 ppm P1 10.00 usec
7.5 7.4 7.3 7.2 7.1 ppm PL1 0.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1301123 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00

10 9 8 7 6 5 4 3 2 1 ppm CX 20.00 cm
CY 10.50 cm
F1P 5.882 ppm
1.000
2.058
2.094
1.027
1.003
1.025
1.069
1.075
1.037
2.055
6.053
3.037
3.039 F1 2353.48 Hz
S57
171.45
170.64
170.10
169.39
147.59
129.23
128.33
128.03
125.22
118.65
NAME NHAc C13
85.39
77.32
77.00
76.68
74.19
72.00
67.75
61.38
52.62
48.58
48.37
48.16
47.94
47.73
47.52
47.30
21.38
19.73
19.65
19.58
EXPNO 4
PROCNO 1
Date_ 20090405
Time 18.28
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 108
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 8192
DW 19.900 usec
DE 6.50 usec
TE 298.0 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127934 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S58
7.923
7.823
7.804
7.439
7.421
7.402
7.360
7.341
7.260
5.950
5.927
5.484
5.463
5.454
5.436
5.412
5.406
5.389
5.381
5.356
5.098
5.073
4.904
4.894
4.877
4.867
4.505
4.479
4.474
4.286
4.268
4.260
4.238
4.229
4.167
4.145
4.095
4.090
4.063
4.059
4.002
3.996
2.123
2.103
2.066
2.030
2.009
1.853
1.721
NAME maltose triazole c13
EXPNO 9
PROCNO 1
Date_ 20090307
Time 21.56
INSTRUM spect
PULPROG zg30
4.510
4.505
4.479
4.474
4.298
4.286
4.268
4.260
4.238
4.229
4.191
4.167
4.145
4.095
4.090
4.063
4.059
4.027
4.021
4.002
3.996
3.970
TD 16384
SOLVENT CDCl3
NS 1
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
AQ 1.3664756 sec
RG 114
DW 83.400 usec
DE 6.50 usec
4.5 4.4 4.3 4.2 4.1 4.0 ppm TE 299.1 K
D1 1.50000000 sec
7.823
7.804
7.439
7.421
7.402
7.360
7.341
7.323

5.950
5.927
5.507
5.484
5.463
5.454
5.436
5.412
5.406
5.389
5.381
5.356
5.098
5.073
5.049
4.904
4.894
4.877
4.867
======== CHANNEL f1 ========
NUC1 1H
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1300089 MHz
WDW EM
7.8 7.7 7.6 7.5 7.4 ppm SSB 0
5.8 5.6 5.4 5.2 5.0 ppm LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm
1.000
2.119
3.002
1.043
4.081
1.027
1.056
1.145
6.020
3.134
3.080
3.086
6.047
3.153
3.052
S59
170.54
170.46
170.29
169.87
169.38
169.28
148.35
129.82
128.85
128.56
125.85
117.72
NAME maltose triazole c13
95.90
85.29
77.32
77.00
76.68
75.38
75.20
72.50
70.83
69.99
69.20
68.76
67.93
62.53
61.45
20.78
20.72
20.64
20.55
20.16
EXPNO 10
PROCNO 1
Date_ 20090307
Time 21.58
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 158
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 8192
DW 19.900 usec
DE 6.50 usec
TE 299.1 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127497 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S60
7.957
7.812
7.809
7.791
7.419
7.401
7.381
7.336
7.318
7.300
7.260
6.185
6.176
5.906
5.896
5.894
5.884
5.640
5.627
5.613
4.495
4.485
4.474
4.463
4.422
4.415
4.391
4.384
4.246
4.236
4.215
4.205
2.099
2.024
NAME ribose triazole
EXPNO 1
PROCNO 1
Date_ 20090314
Time 16.19
6.185
6.176
5.906
5.896
5.894
5.884
5.640
5.627
5.613
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
AQ 1.3664756 sec
RG 40.3
6.1 6.0 5.9 5.8 5.7 ppm DW 83.400 usec
DE 6.50 usec
7.812
7.809
7.791
7.419
7.401
7.381
7.336
7.318
7.300
7.260
4.495
TE 299.9 K
4.485
4.474
4.463
4.422
4.415
4.391
4.384
4.246
4.236
4.215
4.205
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
7.8 7.7 7.6 7.5 7.4 ppm
4.5 4.4 4.3 ppm SI 16384
SF 400.1300088 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm CX 20.00 cm
CY 10.50 cm
F1P 8.128 ppm
1.000
2.016
2.048
1.001
1.011
1.010
1.015
1.029
1.088
1.090
6.075
3.038
F1 3252.12 Hz
S61
170.23
169.32
169.17
147.99
129.89
128.75
128.32
125.65
118.77
NAME PTHALIC-12PH-INDOL
89.92
80.77
77.32
77.00
76.68
74.14
70.57
62.69
20.49
20.30
20.23
EXPNO 3
PROCNO 1
Date_ 20090321
Time 20.57
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 68
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 4096
DW 19.900 usec
DE 6.50 usec
TE 300.2 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127604 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S62
8.333
7.259
5.933
5.911
5.455
5.432
5.410
5.391
5.367
5.261
5.236
5.213
4.445
4.428
4.410
4.392
4.328
4.315
4.296
4.284
4.165
4.162
4.134
4.130
4.039
4.034
4.027
4.022
4.014
4.009
4.002
3.997
2.081
2.063
2.023
1.885
1.422
1.405
1.387
NAME NHac
EXPNO 2
PROCNO 1
Date_ 20090405
Time 18.17
INSTRUM spect
PULPROG zg30
TD 16384
1.422
1.405
1.387
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
5.933
5.911
5.455
5.432
5.410
5.391
5.367
5.261
5.236
5.213
AQ 1.3664756 sec
4.445
4.428
4.410
4.392
4.328
4.315
4.296
4.284
4.165
4.162
4.134
4.130
4.039
4.034
4.027
4.022
4.014
4.009
4.002
RG 161.3
DW 83.400 usec
DE 6.50 usec
TE 298.0 K
D1 1.50000000 sec
1.4 ppm MCREST 0.00000000 sec
======== CHANNEL f1 ========
NUC1 1H
5.8 5.6 5.4 ppm 4.4 4.3 4.2 4.1 4.0 ppm P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
SI 16384
SF 400.1300095 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm 1D
CX
NMR plot parameters
20.00 cm
CY 10.50 cm
F1P 2.215 ppm
1.000
1.033
2.017
1.058
2.072
1.096
1.101
1.100
3.000
3.014
3.007
3.004
3.076
F1 886.46 Hz
S63
170.37
169.78
169.25
168.86
160.11
140.85
126.01
NAME propargy ester triazole
85.84
77.32
77.00
76.68
75.25
72.31
70.39
67.53
61.49
61.40
20.57
20.43
20.04
14.19
EXPNO 5
PROCNO 1
Date_ 20090404
Time 20.39
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 83
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 8192
DW 19.900 usec
DE 6.50 usec
TE 297.8 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6242995 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127520 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S64
7.843
7.259
5.903
5.882
5.462
5.438
5.418
5.398
5.374
5.251
5.227
5.204
4.737
4.270
4.258
4.239
4.226
4.118
4.087
4.076
4.024
4.017
4.013
3.999
3.992
3.423
2.021
2.017
1.981
1.818
NAME -propargy triazole
EXPNO 1
PROCNO 1
Date_ 20090326
Time 20.50
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
AQ 1.3664756 sec
RG 45.3
4.270
4.258
4.239
4.226
4.118
4.087
4.076
4.024
4.017
4.013
3.999
3.992
DW 83.400 usec
5.903
5.882
5.462
5.438
5.418
5.398
5.374
5.251
5.227
5.204
DE 6.50 usec
TE 298.7 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
PL1 0.00 dB
4.3 4.2 4.1 4.0 ppm SFO1 400.1326008 MHz
5.8 5.6 5.4 ppm
SI 16384
SF 400.1300095 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00
10 9 8 7 6 5 4 3 2 1 ppm CX 20.00 cm
CY 10.50 cm
F1P 6.065 ppm
1.000
1.073
2.044
1.021
2.094
1.071
1.067
1.031
1.027
6.095
3.103
3.098
F1 2426.88 Hz
S65
170.50
169.89
169.36
169.05
148.50
120.19
85.61
77.32
77.00
76.68
74.96
72.58
70.30
67.65
61.50
56.27
20.59
20.47
20.43
20.10
NAME prp-alcohol-sug
EXPNO 1
PROCNO 1
Date_ 20100107
Time 21.48
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 207
DS 0
SWH 25062.656 Hz
FIDRES 0.382426 Hz
AQ 1.3074932 sec
RG 4096
DW 19.950 usec
DE 6.50 usec
TE 297.1 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========

NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6243390 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 100.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127528 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40
S66
7.803
7.260
5.871
5.849
5.422
5.415
5.407
5.399
5.393
5.255
5.230
5.171
5.147
5.102
5.078
5.054
4.994
4.973
4.970
4.950
4.916
4.884
4.801
4.769
4.543
4.523
4.313
4.300
4.294
4.282
4.268
4.263
4.252
4.192
4.186
4.161
4.140
4.136
4.109
4.104
2.095
2.056
2.048
2.016
1.998
1.960
1.941
1.875
0.041
NAME prp-triaz
EXPNO 1
PROCNO 1
Date_ 20100428
4.543
4.523
4.313
4.300
4.294
4.282
4.268
4.263
4.252
4.192
4.186
4.161
4.155
4.140
4.136
4.109
4.104
4.083
4.024
4.019
4.012
4.007
3.998
3.994
3.986
3.762
3.756
3.751
3.745
3.737
3.731
3.727
3.720
Time 16.36
INSTRUM spect
PULPROG zg30
TD 16384
SOLVENT CDCl3
NS 16
DS 0
SWH 5995.204 Hz
FIDRES 0.365918 Hz
4.5 4.4 4.3 4.2 4.1 4.0 ppm 3.75 ppm AQ 1.3664756 sec
RG 22
DW 83.400 usec
5.871
5.849
5.422
5.415
5.407
5.399
5.393
5.255
5.230
5.207
5.194
5.171
5.147
5.102
5.078
5.054
4.994
4.973
4.970
4.950
4.916
4.884
4.801
4.769
DE 8.00 usec
TE 673.2 K
D1 1.50000000 sec
======== CHANNEL f1 ========

NUC1 1H
P1 10.00 usec
PL1 0.00 dB
SFO1 400.1326008 MHz
5.8 ppm 5.4 5.3 5.2 5.1 5.0 4.9 4.8 ppm
SI 16384
SF 400.1300091 MHz
WDW EM
SSB 0
LB 0.10 Hz
GB 0
PC 1.00

10 9 8 7 6 5 4 3 2 1 ppm CX
CY
20.00
12.80
cm
cm
F1P 2.164 ppm
F1 865.96 Hz
1.000
1.055
2.032
1.088
1.097
1.042
1.075
1.002
1.049
1.032
2.054
2.014
1.040
1.090
3.029
3.046
3.029
3.036
3.093
3.070
3.003
3.053
S67
170.66
170.37
170.16
169.78
169.35
169.32
169.04
144.18
121.87
98.71
85.79
77.32
77.20
77.00
76.68
75.16
72.60
72.35
71.71
71.02
70.36
68.34
67.61
61.82
61.71
61.44
20.70
20.58
20.52
20.45
20.03
NAME prp-triaz
0.94
EXPNO 2
PROCNO 1
Date_ 20100428
Time 16.39
INSTRUM spect
PULPROG zgpg30
TD 65536
SOLVENT CDCl3
NS 84
DS 0
SWH 25125.629 Hz
FIDRES 0.383387 Hz
AQ 1.3042164 sec
RG 4096
DW 19.900 usec
DE 8.00 usec
TE 673.2 K
D1 2.00000000 sec
d11 0.03000000 sec
======== CHANNEL f1 ========
NUC1 13C
P1 8.90 usec
PL1 5.00 dB
SFO1 100.6243390 MHz
======== CHANNEL f2 ========

CPDPRG2 waltz16
NUC2 1H
PCPD2 90.00 usec
PL2 0.00 dB
PL12 19.10 dB
PL13 22.10 dB
SFO2 400.1319000 MHz
SI 32768
SF 100.6127509 MHz
WDW EM
SSB 0
LB 1.00 Hz
220 200 180 160 140 120 100 80 60 40 20 ppm GB 0
PC 1.40

Desde Acetilado Con TMSN3-FeCl3

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Desde Acetilado Con TMSN3-FeCl3

Uploaded by

Copyright:

Available Formats

Electronic Supplementary Material (ESI) for Chemical Communications

This journal is © The Royal Society of Chemistry 2011

Iron (III) Chloride as an Efficient Catalyst for Stereoselective

Santosh B. Salunke,b,c N.Seshu Babua,c and Chien-Tien Chena∗

azido glycosides 1-10; Detailed procedures for FeCl3:Cu catalyzed dipolar

cycloaddition and analytical data for glycosyl 1,2,3-triazole conjugates 11-16;

General experimental methods, Caution, and Attention------------------------------S2-S3

Table S1: Effect of solvents on the azido glycosylation of β-glucose peracetate------S4

General. 1H NMR and 13

dried over Na with benzophenone-ketyl intermediate under nitrogen atmosphere and

derivatives of glucose1, glactose2, mannose3, ribose, xylose4, maltose, lactose5,

group) in the presence of 10 mol% of Sodium acetate under reflux condition.

N-protected glucosamine derived substrates and propargyl-O-linked glucose

peracetate7 were synthesized by using literature methods.

adverse effects during our studies at small scale reactions.

CH2Cl2 to form explosive azidochloromethane and/or diazidomethane.9 It has been

derivatives in the subsequent azide-alkyne cycloaddition reactions. However, we did

not observe these side products under our catalytic conditions.

Table S1. Effect of solvents on the azido glycosylation of glucose β-peracetate.a

Entry Solvent Time (h) Conversion (%)b Yield (%)c

2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-glucopyranosyl azide (1).10

reaction was monitored by TLC. After complete consumption of starting material in 6

purified by column chromatography (EtOAc/hexanes, 1/2) on silica gel to afford 89

mg (96%) of 2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-glucopyranosyl azide 1 as a white

2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-galactopyranosyl azide (2).10

was monitored by TLC. After complete consumption of starting material in 6 h, the

chromatography (EtOAc/hexanes, 1/2) on silica gel to afford 89 mg (96%) of

2,3,4,6-tetra-O-acetyl-6-deoxy-β-D-galactopyranosyl azide 2 as a white solid. 1H

1.0, CHCl3) (lit.10 [α]23D -14 (c 1.0, CHCl3)).

2,3,4,6-tetra-O-acetyl-6-deoxy-α-D-mannopyranosyl azide (3).12

AcO OAc AcO OAc

was monitored by TLC. After complete consumption of starting material in 7 h, the

chromatography (EtOAc/hexanes, 1/2) on silica gel to afford 83 mg (89%) of

2,3,4,6-tetra-O-acetyl-6-deoxy-α-D-mannopyranosyl azide 3 as a white solid. 1H

+184 (c 1.0, CHCl3)).

2,3,5-tri-O-acetyl-β-D-ribofurunosyl azide (4).14

O OAc 5 mol% FeCl3 O N3

(2S,3R,4R,5R)-5-(acetoxymethyl)tetrahydrofuran-2,3,4-triyl triacetate (79.5 mg, 0.25

complete consumption of starting material in 1.5 h, the reaction mixture was

chromatography (EtOAc/hexanes, 1/2) on silica gel to afford 72 mg (96%) of

2,3,5-tri-O-acetyl-β-D-ribofurunosyl azide 4 as a colorless oil. 1H NMR (400 MHz,

+111.3 (c 1.0, CHCl3) (lit.14 [α]23D +116 (c 1.0, CHCl3)).

2,3,5-tri-O-acetyl-β-D-xylopyranosyl azide (5).10

solution of (2S,3S,4S)-tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (79.5 mg, 0.25

complete consumption of starting material in 3 h, the reaction mixture was quenched

reduced pressure. The crude reside was purified by column chromatography

(EtOAc/hexanes, 1/2) on silica gel to afford 69 mg (92%) of 2,3,5-tri-O-acetyl-β-D-

CHCl3) (lit.15 [α]25D +86 (c 1.0, CHCl3)).

tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2,3,4-triyl triacetate (169.5 mg,

After complete consumption of starting material in 24 h, the reaction mixture was

chromatography (EtOAc/hexanes, 3/2) on silica gel to afford 149 mg (90%) of

hyl)tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2,3,4-triyl triacetate (169.5 mg,

After complete consumption of starting material in 22 h, the reaction mixture was

chromatography (EtOAc/hexanes, 3/2) on silica gel to afford 152 mg (92%) of

-yloxy)tetrahydro-2H-pyran-2-yloxy)tetrahydro-2H-pyran-2,3,4-triyl triacetate (241.5

After complete consumption of starting material in 28 h, the reaction mixture was

chromatography (EtOAc/hexanes, 3/2) on silica gel to afford 206 mg (87%) of

3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl azide (9).18

reaction was monitored by TLC. After complete consumption of starting material in

purified by column chromatography (EtOAc/hexanes, 3/2) on silica gel to afford 105

mg (91%) of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl azide 9 as

[α]25D +39.6 (c 1.0, CHCl3) (lit.18b [α]25D +38 (c 1.0, CHCl3)).

3,4,6-tri-O-acetyl-2-N-acetyl-2-deoxy-β-D-glucopyranosyl azide (10).10