Evaluation of bis-triphenylphosphano-copper(I)-butyrate (C 3H7COOCu(PPh3)2) as catalyst for the synthesis of 1-glycopyranosyl-4-substituted-1,2,3-triazoles

Article abstract of DOI:10.1016/j.carres.2012.01.004

Bis-triphenylphosphano-copper(I)-butyrate (C₃H ₇COOCu(PPh₃)₂) was applied for the synthesis of O-peracylated 1-glycopyranosyl-4-substituted-1,2,3-triazoles from the corresponding glycosyl azides and alkynes. Thi

Full text of DOI:10.1016/j.carres.2012.01.004

Carbohydrate Research 351 (2012) 42–48
Contents lists available at SciVerse ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Note
Evaluation of bis-triphenylphosphano-copper(I)-butyrate
(C3H7COOCu(PPh3)2) as catalyst for the synthesis of
1-glycopyranosyl-4-substituted-1,2,3-triazoles
Éva Bokor a, Csenge Koppány a, Zsombor Gonda b, Zoltán Novák b, László Somsák a,
⇑
a Department of Organic Chemistry, University of Debrecen, H-4010, P.O. Box 20, Debrecen, Hungary
b Department of Organic Chemistry, Eötvös Loránd University, H-1518, P.O. Box 32, Budapest, Hungary
a r t i c l e i n f o
a b s t r a c t
Article history:
Bis-triphenylphosphano-copper(I)-butyrate (C3H7COOCu(PPh3)2) was applied for the synthesis of O-per-
acylated 1-glycopyranosyl-4-substituted-1,2,3-triazoles from the corresponding glycosyl azides and
Received 30 November 2011
Received in revised form 8 January 2012
Accepted 9 January 2012
alkynes. This catalyst proved superior to the CuSO4/
and less reactive glycosyl azides.
L-ascorbic acid system even with sterically hindered
Available online 18 January 2012
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Azide–alkyne cycloaddition
Glycopyranosyl azide
1-Glycopyranosyl-1,2,3-triazole
1. Introduction
enediamine18 proved advantageous. CuI is another often applied
catalyst in the presence of either DIPEA or Et3N with TBTA
(N,N,N-tris-[(1-benzyl-1H-1,2,3-triazole-4-yl)methy]amine).19,20
The regioselective formation of 1,4-disubstituted-1,2,3-tria-
zoles by Cu(I) catalysed azide–alkyne cycloaddition (CuAAC) is a
reliable and robust transformation characterized by high func-
tional group tolerance and simple work-up.1 The widespread use
of this reaction is, among others, also related to the increasing
interest in the 1,2,3-triazole ring as a pharmacophore.2 The wide
variety of conditions used to perform CuAAC include numerous
Cu(I) sources such as inorganic salts of copper(I) in the presence
of a base and/or a ligand stabilizing the Cu(I) oxidation state,
Cu(I) complexes or Cu(II) salts coupled with reducing agents.1
Development of CuAAC generated remarkable attention in the field
of carbohydrate chemistry, as well. Synthesis as well as application
of 1,2,3-triazole containing simple glycosides, oligosaccharides,
glycomacrocycles, glycoclusters, glycodendrimers, glycopeptides,
glycoarrays, glycopolimers and glycosylated biomolecules were
surveyed in several reviews.3–6
In addition, phosphorous containing copper complexes such as
(EtO)3PCuI21 and CuBr(PPh3)3
lysts for this purpose.
proved to be also suitable cata-
22,23
We have reported on the syntheses of three series of 1-(D-gluco-
pyranosyl)-4-substituted-1,2,3-triazoles24 4–6 (Table 1) which
were tested as inhibitors of glycogen phosphorylase enzyme
(GP), a validated molecular target for the treatment of type 2 dia-
betes. Several b-D-glucopyranosyl derivatives (O-deprotected 4)
proved to be low micromolar inhibitors of GP. Furthermore, their
inhibition constants as well as binding modes (revealed by X-ray
crystallography) showed a remarkable similarity to those of the
corresponding b-D
-glucopyranosylamide type inhibitors,25 thereby
providing a new example of the amide-1,2,3-triazole bioisosteric
relationship,26–28 and a new potential biological application of 1-
glycosyl-1,2,3-triazoles. Regioselective syntheses of the O-peracy-
lated derivatives 4–6 were carried out in CuAAC reactions of the
1-Glycosyl-1,2,3-triazole derivatives were obtained from rela-
tively easily available glycosyl azides by using diverse Cu(I)
sources. In situ reduction of Cu(II) salts, usually CuSO4 or Cu(OAc)2
by Na-ascorbate or
is one of the most commonly used possibilities for the catalysis,
corresponding
D-glucopyranosyl azides 1–3 with terminal alkynes
in water in the presence of CuSO4 and
L-ascorbic acid (Table 1, con-
L
-ascorbic acid7–16 as well as by Cu turnings11,17
ditions i). However, under these conditions the desired triazoles
could be obtained only in low yields and with incomplete conver-
sions of the starting materials in several cases. Changing the sol-
vent to aqueous CH3NO2 or DMSO, and increasing the catalyst
load up to 11 mol % did not bring about significant improve-
ments.24 Recently, bis-triphenylphosphano-copper(I)-butyrate
whereby, with unprotected glycosyl azides, addition of o-phenyl-
⇑
Corresponding author. Tel.: +36 52 512 900/22348; fax: +36 52 512 744.
E-mail address: somsak@tigris.unideb.hu (L. Somsák).
(C3H7COOCu(PPh3)2) was developed as
a new, highly active
0008-6215/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2012.01.004

É. Bokor et al. / Carbohydrate Research 351 (2012) 42–48
43
Table 1
Comparison of catalysts in reactions of D-glucopyranosyl azides and alkynes
R
C
C
H
N
N
N
a-d
i or ii
Glc-N3
Glc
R
1-3
4-6
i24) CuSO4, L-ascorbic acid,a H2O, 70 ºC, 8 h; ii) C3H7COOCu(PPh3)2, CH2Cl2, rt
Glc
Alkyne
R
Product
Conditions
i
ii
Yield (%)
Catalyst (mol %)
Reaction timeb
Yield (%)
a
b
–CH2OH
–CH2OAc
4a
4b
65
2
1
1 day
1 h
90
96
OAc
O
Not investigated
AcO
AcO
1
2
3
c
d
–CO2Et
Phenyl
4c
4d
89
58
1
1
1 h
10 min
92
95
OAc
a
b
c
d
–CH2OH
–CH2OAc
–CO2Et
Phenyl
5a
5b
5c
No reaction
5
1
1
1
1 day
8 h
4 h
4 h
89
97
90
92
OBz
O
Not investigated
BzO
BzO
56c
BzO
5d
No reaction
CONH2
a
b
c
d
–CH2OH
–CH2OAc
–CO2Et
Phenyl
6a
6b
6c
36
8
2
2
5
1 day
5 h
1 day
1 day
Tracesd
87
OAc
O
Not investigated
72
39
AcO
AcO
91
76e
AcO
6d
a
b
c
1.5 mol % CuSO4, 20 mol % L-ascorbic acid for 4, 7.5 mol % CuSO4, 20 mol % L
-ascorbic acid for 5 and 6 were used.24
Necessary for complete consumption of the starting materials 1–3.
Conversion: 63%.24
d
e
Reported yield by a different method: 60%.11
Reported yield by a different method: 63%.11
catalyst for the CuAAC reaction. By using this complex, several 1,4-
disubstituted-1,2,3-triazoles were synthesised in excellent
yields.29 In view of the efficiency of this catalyst, the aim of our
present work has been to investigate its applicability for the syn-
thesis of the above and other 1-glycosyl-1,2,3-triazoles.
The Cu(I)-butyrate complex was also applied for the syntheses
of further O-peracetylated 1-glycopyranosyl-4-substituted-1,2,3-
triazoles from the corresponding glycosyl azides 7–13 (Table 2).
For the formation of b-
deoxy-b- -glucopyranosyl-1,2,3-triazoles 14 and 15 1 mol % of
the catalyst was as effective as in the b- -glucopyranosyl series
4. In a similar manner, reaction of 2-deoxy-2-phtalimido-b- -glu-
D
-xylopyranosyl- and 20-acetamido-20-
D
D
D
2. Results and discussion
copyranosyl azide 9 with phenylacetylene worked well in the pres-
ence of 1 mol % catalyst to give 16d in excellent yield, while
cycloaddition with the bulky 2-ethynylnaphtalene e proceeded
only with higher catalyst load (2 mol %). Synthesis of (20-deoxy-
First, the efficiency of C3H7COOCu(PPh3)2 was probed in reac-
tions between peracylated glycopyranosyl azides 1–3 and terminal
alkynes a–d bearing free hydroxyl, ester, as well as aromatic
groups. The experiments were performed according to the litera-
ture procedure29 in dichloromethane at room temperature (Table 1,
conditions ii). In the reactions with propargyl alcohol (a) the cop-
per(I)-butyrate proved to be efficient in 2 and 5 mol % ratio for
the syntheses of 4a and 5a, respectively, while even 8 mol % of
20-phtalimido-
a
-D
-glucopyranosyl)-4-phenyl-1,2,3-triazole
17d
required higher catalyst concentration and longer reaction time
compared to its b counterpart 16d, similarly to observations with
a–b pairs earlier (4 versus 6). The observed differences in the reac-
tivity of the anomeric pairs of glycosyl azides are in accord with lit-
erature experiences, and may be explained by the higher steric
hindrance of the azido group in a-position or by the different dipo-
the catalyst was insufficient to obtain 6a. Alkynes b–d with b-D-
glucopyranosyl azides 1 and 2 required 1 mol % catalyst load. Gen-
erally, syntheses of compounds 5 required longer reaction time as
compared to those of derivatives 4, presumably because of the ste-
rically more crowded environment of the azido group in 2. How-
ever, it has to be noted, that in aqueous medium in the presence
lar character of the anomeric azides arising from the anomeric
effect.8,11,24
The behaviour of glycopyranosyl azides 11–13 with an axial
substituent in position 4 was different from that of the previously
studied 1,2-trans glycopyranosyl azides (1, 7–9). Contrary to other
of CuSO4/L-ascorbic acid (conditions i) transformation of the O-
b azides, transformation of the b-D-galacto configured 11 into the
perbenzoylated (b-
D
-gluco-hept-2-ulopyranosylazide)onamide (2)
corresponding triazoles 18 needed longer reaction time. The
a-L-
occurred only with ethyl propiolate, and under modified reaction
conditions in DMSO the conversions were also not complete.24
Somewhat higher amount of the catalyst and longer reaction time
arabinopyranosyl azide 12 provided similar results, however,
1 mol % catalyst load was sufficient for the synthesis of 19b and
19d. Results with the b- -fucopyranosyl derivatives 20 are similar
L
were needed to obtain
a-D-glucopyranosyl-1,2,3-triazole deriva-
to experiences in the -D-glycopyranosyl cases 6, 17 that is, to
a
tives 6b,c (2 mol %) and 6d (5 mol %) from the less reactive
azide8,11,24 3. Yields were around or above 90% in almost each case
demonstrating the superior performance of C3H7COOCu(PPh3)2
achieve total consumption of the starting material 13 the catalyst
concentration had to be increased to 2–5 mol %. These observations
are in line with literature experiences where b-D-manno and b-D-
over the CuSO4/L-ascorbic acid system (compare yields under
galacto configured glycopyranosyl azides with axial substituents
headings i and ii in Table 1).

44
É. Bokor et al. / Carbohydrate Research 351 (2012) 42–48
gave the 1,2,3-triazoles under longer reaction times and/or in low-
4.2.3. Ethyl 1-(20,30,40,60-tetra-O-acetyl-b-
D-glucopyranosyl)-
1,2,3-triazole-4-carboxylate (4c)
er yields as compared to the b-
D
-glucopyranosyl counterparts.13,17
From 1 (0.1 g, 0.27 mmol), ethyl propiolate (28
lL, 0.27 mmol)
and C3H7COOCu(PPh3)2 (1.8 mg, 2.7 mol) according to Section 4.2.
l
3. Conclusion
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.12 g (92%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.24
Application of the C3H7COOCu(PPh3)2 complex as a highly
active catalyst in CuAAC reactions with a variety of glycosyl azides
gave the corresponding 1,2,3-triazoles in excellent yields. The pres-
ence of a free hydroxyl group in the alkyne, increasing steric hin-
drance or diminished reactivity as well as the presence of an
axial substituent in the pyranoid ring of the glycosyl azide required
higher catalyst load and/or extended reaction times. Generally, this
catalyst has broader applicability with glycosyl azides than the
4.2.4. 4-Phenyl-1-(20,30,40,60-tetra-O-acetyl-b-
D-glucopyranosyl)-
1,2,3-triazole (4d)
From 1 (0.1 g, 0.27 mmol), phenylacetylene (29
lL, 0.27 mmol)
and C3H7COOCu(PPh3)2 (1.8 mg, 2.7 mol) according to Section 4.2.
l
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.12 g (95%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.7,11,19
commonly used CuSO4/L-ascorbic acid system.
4.2.5. [4-Hydroxymethyl-1-(30,40,50,70-tetra-O-benzoyl-b-
D-gluco-
hept-2-ulopyranosyl)-1,2,3-triazole]onamide (5a)
4. Experimental
From 2 (0.1 g, 0.15 mmol), propargyl alcohol (9
lL, 0.15 mmol)
4.1. General methods
and C3H7COOCu(PPh3)2 (5.1 mg, 7.6 mol) according to Section 4.2.
l
Purified by column chromatography (2:1 EtOAc–hexane) to yield
0.10 g (89%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.24
Melting points were measured in open capillary tubes or on a
Kofler hot-stage and are uncorrected. Optical rotations were
determined with a Perkin–Elmer 241 polarimeter at rt. NMR
spectra were recorded with Bruker 360 (360/90 MHz for 1H/13C)
spectrometer. Chemical shifts are referenced to Me4Si (1H), or
to the residual solvent signals (13C). TLC was performed on DC-
Alurolle Kieselgel 60 F254 (Merck), and the plates were visualised
under UV light and by gentle heating. For column chromatogra-
phy Kieselgel 60 (Merck, particle size 0.063–0.200 mm) was used.
Dichloromethane was distiled from P4O10 and stored over 4 Å
molecular sieves. Propargyl alcohol (a), propargyl acetate (b),
ethyl propiolate (c) and phenylacetylene (d) were purchased from
Aldrich. 2-Ethynylnaphthalene30 (e) and the per-O-acylated gly-
copyranosyl azides31–35 1–3 and 7–13 as well as the complex29
C3H7COOCu(PPh3)2 were synthesized according to published
procedures.
4.2.6. [4-Acetoxymethyl-1-(30,40,50,70-tetra-O-benzoyl-b-
D-gluco-
hept-2-ulopyranosyl)-1,2,3-triazole]onamide (5b)
From 2 (0.1 g, 0.15 mmol), propargyl acetate (15
and C3H7COOCu(PPh3)2 (1.0 mg, 1.5 mol) according to Section 4.2.
Purified by column chromatography (1:1 EtOAc–hexane) to yield
0.11 g (97%) of colourless oil. Rf: 0.51 (5:4 EtOAc–hexane); [
lL, 0.15 mmol)
l
a
]
D
ꢀ9 (c 0.56, CHCl3); 1H NMR (CDCl3): d (ppm) 8.10–7.23 (21H, m,
aromatics, triazole CH), 6.97 (1H, s, CONH2), 6.56 (1H, s, CONH2),
6.33 (1H, pseudo t, J = 8.0, 8.0 Hz, H-40 or H-50), 6.17 (1H, d,
J = 8.0 Hz, H-30), 5.89 (1H, pseudo t, J = 9.2, 8.6 Hz, H-40 or H-50),
5.23 (1H, ddd, J = 9.9, 3.7, <1 Hz, H-60), 5.10 (2H, s, CH2), 4.89
(1H, dd, J = 12.3, <1 Hz, H-70a), 4.57 (1H, dd, J = 12.3, 3.7 Hz, H-
70b), 2.00 (3H, s, CH3); 13C NMR (CDCl3): d (ppm) 170.5, 166.2,
166.1, 165.0, 164.9, 164.2 (CO), 142.9 (triazole C-4), 133.7–128.2
(aromatics), 122.5 (triazole C-5), 89.4 (C-20), 73.9, 72.2, 71.0, 68.1
(C-30–C-60), 62.3 (C-70), 57.1 (CH2), 20.6 (CH3). Anal. Calcd for
C40H34N4O12 (762.74): C, 62.99; H, 4.49; N, 7.35. Found: C, 63.11;
H, 4.63; N, 7.24.
4.2. General procedure for the synthesis of O-peracylated 1-
glycopyranosyl-4-substituted-1,2,3-triazoles in the presence of
C3H7COOCu(PPh3)2 catalyst
An azide (1–3 or 7–13, 0.1 g) and an equimolar amount of an al-
kyne (a–e) were dissolved in anhydrous CH2Cl2 (2 mL), C3H7COOC-
u(PPh3)2 (1–5 mol %, Tables 1 and 2) catalyst was added, the
mixture was stirred at rt and monitored by TLC (1:1 EtOAc–hex-
ane). After completion of the reaction (Tables 1 and 2), the solvent
was evaporated and the residue was purified by column
chromatography.
4.2.7. [4-Ethoxycarbonyl-1-(30,40,50,70-tetra-O-benzoyl-b-
D-gluco-
hept-2-ulopyranosyl)-1,2,3-triazole]onamide (5c)
From 2 (0.1 g, 0.15 mmol), ethyl propiolate (15
lL, 0.15 mmol)
and C3H7COOCu(PPh3)2 (1.0 mg, 1.5 mol) according to Section 4.2.
l
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.10 g (90%) of colourless oil.1H and 13C NMR data correspond to
the reported spectra.24
4.2.1. 4-Hydroxymethyl-1-(20,30,40,60-tetra-O-acetyl-b-
D-
glucopyranosyl)-1,2,3-triazole (4a)
4.2.8. [4-Phenyl-1-(30,40,50,70-tetra-O-benzoyl-b-
D-gluco-hept-2-
ulopyranosyl)-1,2,3-triazole]onamide (5d)
From 1 (0.1 g, 0.27 mmol), propargyl alcohol (16
lL, 0.27 mmol)
and C3H7COOCu(PPh3)2 (3.6 mg, 5.4 mol) according to Section 4.2.
l
From 2 (0.1 g, 0.15 mmol), phenylacetylene (17
lL, 0.15 mmol)
Purified by column chromatography (2:1 EtOAc–hexane) to yield
0.10 g (90%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.8,11
and C3H7COOCu(PPh3)2 (1.0, 1.5 mol) according to Section 4.2.
l
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.11 g (92%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.24
4.2.2. 4-Acetoxymethyl-1-(20,30,40,60-tetra-O-acetyl-b-
D-
glucopyranosyl)-1,2,3-triazole (4b)
4.2.9. 4-Acetoxymethyl-1-(20,30,40,60-tetra-O-acetyl-
a-D-
From 1 (0.1 g, 0.27 mmol), propargyl acetate (27
lL, 0.27 mmol)
glucopyranosyl)-1,2,3-triazole (6b)
and C3H7COOCu(PPh3)2 (1.8 mg, 2.7 mol) according to Section 4.2.
l
From 3 (0.1 g, 0.27 mmol), propargyl acetate (27
and C3H7COOCu(PPh3)2 (3.6 mg, 5.4 mol) according to Section 4.2.
Purified by column chromatography (1:1 EtOAc–hexane) to yield
0.11 g (87%) of white solid. Mp: 139–141 °C; [ +92 (c 0.51,
CHCl3); 1H NMR (CDCl3): d (ppm) 7.74 (1H, s, triazole CH), 6.37
lL, 0.27 mmol)
Purified by column chromatography (1:1 EtOAc–hexane) to yield
l
0.12 g (96%) of white solid. Mp: 151–153 °C (lit.8 mp: 143–
144 °C); [
a
]
D ꢀ24 (c 0.57, CHCl3); 1H and 13C NMR data correspond
a
]
D
to the reported spectra.8

É. Bokor et al. / Carbohydrate Research 351 (2012) 42–48
45
Table 2
Synthesis of 1-glycopyranosyl-4-substituted-1,2,3-triazoles
R
C C H
b, d, e
N
N
N
Gly-N3
7-13
Gly
R
C3H7COOCu(PPh3)2
CH2Cl2, rt
14-20
Gly
Alkyne
R
Conditions
Product
Catalyst (mol %)
Reaction time
Yield (%)
b
d
e
–CH2OAc
Phenyl
2-Naphthyl
14b
14d
14e
1
1
1
2 h
10 min
10 min
96
93
86
O
AcO
AcO
7
8
OAc
b
d
e
–CH2OAc
Phenyl
2-Naphthyl
15b
15d
15e
1
1
1
1 h
30 min
30 min
88
OAc
O
94a
AcO
AcO
85
NHAc
d
e
Phenyl
2-Naphthyl
16d
16e
1
2
10 min
6 h
99
96
OAc
O
AcO
AcO
9
NPht
OAc
O
AcO
AcO
10
d
Phenyl
17d
5
1 day
98
PhtN
b
d
–CH2OAc
Phenyl
18b
18d
1
2
6 h
8 h
92
AcO
OAc
O
90b
11
AcO
AcO
AcO
Me
OAc
b
d
–CH2OAc
Phenyl
19b
19d
1
1
2 h
5 h
96
98
O
12
13
OAc
b
d
–CH2OAc
Phenyl
20b
20d
2
5
4 h
2 h
96
97
O
OAc
OAc
OAc
a
Reported yield by a different method: 90%.12
Reported yield by different methods: 74%;19 91%.16
b
(1H, d, J = 6.2 Hz, H-10), 6.25 (1H, pseudo t, J = 9.9, 9.2 Hz, H-30 or H-
40), 5.33 (1H, dd, J = 9.9, 6.2 Hz, H-20), 5.27–5.21 (3H, m, H-30 or H-
40, CH2), 4.39 (1H, ddd, J = 10.5, 3.7, <1 Hz, H-50), 4.27 (1H, dd,
J = 12.3, 3.7 Hz, H-60a), 4.04 (1H, dd, J = 12.3, <1 Hz, H-60b), 2.10,
2.07 (2), 2.04, 1.88 (5 ꢁ 3H, 5s, OCOCH3); 13C NMR (CDCl3): d
(ppm) 170.6, 170.3, 170.0, 169.5 (2) (COCH3), 142.4 (triazole C-4),
125.8 (triazole C-5), 81.3 (C-10), 71.1, 70.2, 69.6, 67.8 (C-20–C-50),
61.1 (C-60), 57.2 (CH2), 20.7, 20.5 (3), 20.1 (COCH3). Anal. Calcd
for C19H25N3O11 (471.42): C, 48.41; H, 5.35; N, 8.91. Found: C,
48.56; H, 5.44; N, 8.78.
4.2.12. 4-Acetoxymethyl-1-(20,30,40-tri-O-acetyl-b-
xylopyranosyl)-1,2,3-triazole (14b)
D
-
From 7 (0.1 g, 0.33 mmol), propargyl acetate (33
l
L, 0.33 mmol)
and C3H7COOCu(PPh3)2 (2.2 mg, 3.3
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.13 g (96%) of white solid. Mp: 160–161 °C; [
lmol) according to Section 4.2.
a]
ꢀ55 (c 0.50,
D
CHCl3); 1H NMR (CDCl3): d (ppm) 7.87 (1H, s, triazole CH), 5.83
(1H, d, J = 8.0 Hz, H-10), 5.47–5.38 (2H, m, H-20, H-30), 5.25–5.14
(3H, m, H-40, CH2), 4.31 (1H, dd, J = 11.1, 5.5 Hz, H-50a), 3.64 (1H,
pseudo t, J = 11.1, 11.1 Hz, H-50b), 2.08 (2), 2.06, 1.89 (4 ꢁ 3H, 4s,
OCOCH3); 13C NMR (CDCl3): d (ppm) 170.6, 169.7, 169.6, 168.8
(OCOCH3), 143.5 (triazole C-4), 122.0 (triazole C-5), 86.1 (C-10),
71.9, 70.4, 68.2 (C-20–C-40), 65.4 (C-50), 57.3 (CH2), 20.6, 20.5,
20.4, 20.0 (OCOCH3). Anal. Calcd for C16H21N3O9 (399.35): C,
48.12; H, 5.30; N, 10.52. Found: C, 48.24; H, 5.17; N, 11.02.
4.2.10. Ethyl 1-(20,30,40,60-tetra-O-acetyl-
a-D-glucopyranosyl)-
1,2,3-triazole-4-carboxylate (6c)
From 3 (0.1 g, 0.27 mmol), ethyl propiolate (28
lL, 0.27 mmol)
and C3H7COOCu(PPh3)2 (3.6 mg, 5.4ꢂ
l
mol) according to Section 4.2.
Purified by column chromatography (4:5 EtOAc–hexane) to yield
0.12 g (91%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.24
4.2.13. 4-Phenyl-1-(20,30,40-tri-O-acetyl-b-
D-xylopyranosyl)-
1,2,3-triazole (14d)
From 7 (0.2 g, 0.66 mmol), phenylacetylene (73
lL, 0.66 mmol)
4.2.11. 4-Phenyl-1-(20,30,40,60-tetra-O-acetyl-
a-D
-
and C3H7COOCu(PPh3)2 (4.5 mg, 6.6 mol) according to Section 4.2.
l
glucopyranosyl)-1,2,3-triazole (6d)
Purified by recrystallisation from EtOH to yield 0.25 g (93%) of
From 3 (0.1 g, 0.27 mmol), phenylacetylene (29
lL, 0.27 mmol)
white solid. Mp: 271–272 °C; [
a]
ꢀ104 (c 0.50, DMSO); 1H NMR
D
and C3H7COOCu(PPh3)2 (9 mg, 14 mol) according to Section 4.2.
l
(DMSO-d6): d (ppm) 8.95 (1H, s, triazole CH), 7.84–7.34 (5H, m,
aromatics), 6.29 (1H, d, J = 8.6 Hz, H-10), 5.64, 5.56 (2 ꢁ 1H, 2 pseu-
do t, J = 9.2, 9.2 Hz in each, H-20, H-30), 5.12 (1H, ddd, J = 10.5, 9.2,
5.5 Hz, H-40), 4.13 (1H, dd, J = 11.1, 5.5 Hz, H-50a), 3.90 (1H, pseudo
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.10 g (76%) of white solid. 1H and 13C NMR data correspond to
the reported spectra.11,24

46
É. Bokor et al. / Carbohydrate Research 351 (2012) 42–48
t, J = 11.1, 10.5 Hz, H-50b), 2.03, 2.01, 1.81 (3 ꢁ 3H, 3s, OCOCH3); 13C
NMR (DMSO-d6): d (ppm) 169.5 (2), 168.6 (OCOCH3), 146.8 (tria-
zole C-4), 130.1, 129.0 (2), 128.2, 125.1 (2) (aromatics), 120.2 (tri-
azole C-5), 84.7 (C-10), 71.7, 70.4, 68.0 (C-20–C-40), 64.0 (C-50), 20.4,
20.3, 19.9 (OCOCH3). Anal. Calcd for C19H21N3O7 (403.39): C, 56.57;
H, 5.25; N, 10.42. Found: C, 56.44; H, 5.37; N, 10.30.
NHCOCH3); 13C NMR (DMSO-d6): d (ppm) 170.0, 169.6 169.5,
169.4, (COCH3), 146.5 (triazole C-4), 133.0, 132.6, 128.6, 128.0,
127.7, 127.6, 126.7, 126.3, 123.6, 123.4 (aromatics), 120.6 (triazole
C-5), 84.9 (C-10), 73.3, 72.2, 68.0 (C-30–C-50), 61.7 (C-60), 52.3 (C-20),
22.3, 20.5, 20.4, 20.3 (COCH3). Anal. Calcd for C26H28N4O8 (524.52):
C, 59.54; H, 5.38; N, 10.68. Found: C, 59.70; H, 5.29; N, 10.81.
4.2.14. 4-(2-Naphthyl)-1-(20,30,40-tri-O-acetyl-b-
D-
4.2.18. 1-(20-Deoxy-20-phtalimido-30,40,60-tri-O-acetyl-b-
D-
xylopyranosyl)-1,2,3-triazole (14e)
glucopyranosyl)-4-phenyl-1,2,3-triazole (16d)
From
7
(0.1 g, 0.33 mmol), 2-ethynylnaphthalene (0.05 g,
mol) according
From 9 (0.3 g, 0.65 mmol), phenylacetylene (71
and C3H7COOCu(PPh3)2 (4.4 mg, 6.5 mol) according to Section 4.2.
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.37 g (99%) of white solid. Mp: 194–196 °C; [
lL, 0.65 mmol)
0.33 mmol) and C3H7COOCu(PPh3)2 (2.2 mg, 3.3
l
l
to Section 4.2. Purified by recrystallisation from EtOH to yield
0.13 g (86%) of white solid. Mp: 285–286 °C; 1H NMR (DMSO-d6):
d (ppm) 9.08 (1H, s, triazole CH), 8.41–7.54 (7H, m, aromatics),
6.33 (1H, d, J = 8.6 Hz, H-10), 5.67, 5.58 (2 ꢁ 1H, 2 pseudo t,
J = 9.2, 9.2 Hz in each, H-20, H-30), 5.14 (1H, ddd, J = 10.5, 9.2,
4.9 Hz, H-40), 4.15 (1H, dd, J = 11.1, 4.9 Hz, H-50a), 3.92 (1H, pseudo
t, J = 11.1, 10.5 Hz, H-50b), 2.05, 2.02, 1.83 (3 ꢁ 3H, 3s, OCOCH3); 13C
NMR (DMSO-d6): d (ppm) 169.5 (2), 168.6 (OCOCH3), 146.8 (tria-
zole C-4), 132.9, 132.6, 128.6, 127.9, 127.6, 127.5, 126.6, 126.2,
123.6, 123.4 (aromatics), 120.5 (triazole C-5), 84.7 (C-10), 71.7,
70.4, 67.9 (C-20–C-40), 64.0 (C-50), 20.4, 20.2, 19.8 (OCOCH3). Anal.
Calcd for C23H23N3O7 (453.44): C, 60.92; H, 5.11; N, 9.27. Found:
C, 61.01; H, 5.25; N, 9.18.
a
]
ꢀ107 (c 0.55,
D
CHCl3); 1H NMR (CDCl3): d (ppm) 8.05 (1H, s, triazole CH), 7.83–
7.28 (9H, m, aromatics, Pht), 6.85 (1H, d, J = 10.5 Hz, H-10), 6.06
(1H, J = 10.5, 9.2 Hz), 5.39 (1H, J = 9.9, 9.2 Hz), 4.94 (1H, J = 10.5,
9.9 Hz) (3 pseudo t, H-20, H-30, H-40), 4.40 (1H, dd, J = 12.3, 4.3 Hz,
H-60a), 4.24–4.20 (2H, m, H-50, H-60b), 2.12, 2.09, 1.89 (3 ꢁ 3H, 3s,
OCOCH3); 13C NMR (CDCl3): d (ppm) 170.5, 169.8, 169.3 (COCH3),
167.5, 166.4 (NPhtCO), 148.2 (triazole C-4), 134.6, 134.4, 131.0,
130.5, 129.7, 128.7, 128.4, 125.7, 123.8 (aromatics, Pht), 117.7 (tria-
zole C-5), 83.0 (C-10), 75.0, 70.4, 68.1 (C-30–C-50), 61.6 (C-60), 53.9 (C-
20), 20.6, 20.5, 20.3 (COCH3). Anal. Calcd for C28H26N4O9 (562.53): C,
59.78; H, 4.66; N, 9.96. Found: C, 59.89; H, 4.81; N, 9.90.
4.2.15. 1-(20-Acetamido-20-deoxy-30,40,60-tri-O-acetyl-b-
D
-
4.2.19. 1-(20-Deoxy-20-phtalimido-30,40,60-tri-O-acetyl-b-
D-
glucopyranosyl)-4-acetoxy methyl-1,2,3-triazole (15b)
glucopyranosyl)-4-(2-naphthyl)-1,2,3-triazole (16e)
From 8 (0.2 g, 0.54 mmol), propargyl acetate (53
and C3H7COOCu(PPh3)2 (3.6 mg, 5.4 mol) according to Section 4.2.
Purified by column chromatography (4:1 EtOAc–hexane, then
EtOAc) to yield 0.22 g (88%) of white solid. Mp: 240–241 °C; [
l
L, 0.54 mmol)
From
9
(0.3 g, 0.65 mmol), 2-ethynylnaphthalene (0.1 g,
mol) according
l
0.65 mmol) and C3H7COOCu(PPh3)2 (8.8 mg, 13
to Section 4.2. Purified by column chromatography (2:3 EtOAc–
l
a]
D
hexane) to yield 0.38 g (96%) of white solid. Mp: 194–196 °C;
ꢀ30 (c 0.51, CHCl3); 1H NMR (CDCl3): d (ppm) 7.98 (1H, s, triazole
CH), 6.75 (1H, d, J = 8.8 Hz, NHAc), 6.15 (1H, d, J = 9.6 Hz, H-10), 5.55
(1H, pseudo t, J = 9.6, 9.6 Hz, H-30or H-40), 5.27–5.22 (3H, m, H-30or
H-40, CH2) 4.61 (1H, ddd, J = 9.6, 9.6, 8.7 Hz H-20), 4.30 (1H, dd,
J = 12.3, 4.4 Hz, H-60a), 4.16 (1H, dd, J = 12.3, <1 Hz, H-60b), 4.09
(1H, ddd, J = 8.8, 4.4, <1 Hz, H-50), 2.07 (12H, s, 4 ꢁ OCOCH3), 1.77
(3H, s, NHCOCH3); 13C NMR (CDCl3): d (ppm) 170.6 (4), 169.3,
(COCH3), 143.2 (triazole C-4), 123.0 (triazole C-5), 85.7 (C-10),
74.8, 72.1, 68.0 (C-30–C-50), 61.7 (C-60), 57.3 (CH2), 53.3 (C-20),
22.7, 20.8, 20.6, 20.5 (2) (COCH3). Anal. Calcd for C19H26N4O10
(470.43): C, 48.51; H, 5.57; N, 11.91. Found: C, 48.66; H, 5.65; N,
11.74.
[a]
ꢀ164 (c 0.54, CHCl3); 1H NMR (CDCl3): d (ppm) 8.30–7.45
D
(12H, m, aromatics, Pht, triazole CH), 6.88 (1H, d, J = 10.5 Hz, H-
10), 6.08 (1H, J = 10.5, 9.2 Hz), 5.40 (1H, J = 9.9, 9.2 Hz), 4.97 (1H,
J = 10.5, 9.9 Hz) (3 pseudo t, H-20, H-30, H-40), 4.42 (1H, dd,
J = 12.3, 4.9 Hz, H-60a), 4.26–4.21 (2H, m, H-50, H-60b), 2.13, 2.10,
1.90 (3 ꢁ 3H, 3s, OCOCH3); 13C NMR (CDCl3): d (ppm) 170.5,
169.9, 169.4 (COCH3), 167.6, 166.5 (NPhtCO), 148.3 (triazole C-4),
134.6–123.8 (aromatics, Pht), 118.0 (triazole C-5), 83.1 (C-10),
75.1, 70.4, 68.2 (C-30–C-50), 61.6 (C-60), 54.0 (C-20), 20.7, 20.6,
20.3 (COCH3). Anal. Calcd for C32H28N4O9 (612.59): C, 62.74; H,
4.61; N, 9.15. Found: C, 62.60; H, 4.70; N, 9.04.
4.2.20. 1-(20-Deoxy-20-phtalimido-30,40,60-tri-O-acetyl-
a-D-
glucopyranosyl)-4-phenyl-1,2,3-triazole (17d)
4.2.16. 1-(20-Acetamido-20-deoxy-30,40,60-tri-O-acetyl-b-
D
-
glucopyranosyl)-4-phenyl-1,2,3-triazole (15d)
From 10 (0.1 g, 0.22 mmol), phenylacetylene (24
and C3H7COOCu(PPh3)2 (7.3 mg, 11 mol) according to Section 4.2.
Purified by column chromatography (4:5 EtOAc–hexane) to yield
0.12 g (98%) of white solid. Mp: 161–163 °C; [ +182 (c 0.54,
lL, 0.22 mmol)
From 8 (0.1 g, 0.27 mmol), phenylacetylene (29
and C3H7COOCu(PPh3)2 (1.8 mg, 2.7 mol) according to Section 4.2.
Purified by column chromatography (7:3 EtOAc–hexane, then
l
L, 0.27 mmol)
l
l
a
]
D
MeOH) to yield 0.12 g (94%) of white solid. Mp: 282–284 °C; [
a
]
CHCl3); 1H NMR (CDCl3): d (ppm) 7.91 (1H, s, triazole CH), 7.79–
7.29 (9H, m, aromatics, Pht), 7.17 (1H, pseudo t, J = 10.5, 10.5 Hz,
H-30), 6.44 (1H, d, J = 5.5 Hz, H-10), 5.30 (1H, pseudo t, J = 9.9,
9.2 Hz, H-40), 5.07 (1H, dd, J = 10.5, 5.5 Hz, H-20), 4.70 (1H, ddd,
J = 10.5, 3.1, <1 Hz, H-50), 4.37 (1H, dd, J = 12.3, 3.1 Hz, H-60a), 4.12
(1H, dd, J = 12.3, <1 Hz, H-60b), 2.10, 1.90 (9H, 2s, 3 ꢁ OCOCH3); 13C
NMR (CDCl3): d (ppm) 170.4, 170.1, 168.9 (COCH3), 166.8 (2)
(NPhtCO), 147.3 (triazole C-4), 134.5 (2), 130.7 (2), 129.6, 128.7
(2), 128.4, 125.8 (2), 123.7 (2) (aromatics, Pht), 121.0 (triazole C-
5), 82.8 (C-10), 71.9, 69.6, 67.2 (C-30–C-50), 61.4 (C-60), 53.3 (C-20),
20.6 (3) (COCH3). Anal. Calcd for C28H26N4O9 (562.53): C, 59.78; H,
4.66; N, 9.96. Found: C, 59.68; H, 4.77; N, 10.05.
D
ꢀ71 (c 0.58, DMSO); 1H and 13C NMR data correspond to the re-
ported spectra.12
4.2.17. 1-(20-Acetamido-20-deoxy-30,40,60-tri-O-acetyl-b-
D-
glucopyranosyl)-4-(2-naphthyl)-1,2,3-triazole (15e)
From
8
(0.2 g, 0.54 mmol), 2-ethynylnaphthalene (0.08 g,
mol) according
0.54 mmol) and C3H7COOCu(PPh3)2 (3.6 mg, 5.4
l
to Section 4.2. Purified by column chromatography (7:3 EtOAc–
hexane, then MeOH) to yield 0.24 g (85%) of white solid. Mp:
298–300 °C; [
a]
ꢀ70 (c 0.51, DMSO); 1H NMR (DMSO-d6): d
D
(ppm) 9.00 (1H, s, triazole CH), 8.42 (1H, s, aromatic), 8.17–7.54
(7H, m, aromatics, NHAc), 6.19 (1H, d, J = 9.6 Hz, H-10), 5.42, 5.14
(2 ꢁ 1H, 2 pseudo t, J = 9.6 Hz in each, H-30, H-40), 4.69 (1H, ddd,
J = 9.6, 9.6, 8.8 Hz, H-20), 4.31 (1H, ddd, J = 8.8, 4.4, <1 Hz, H-50),
4.20 (1H, dd, J = 12.3, 4.4 Hz, H-60a), 4.10 (1H, dd, J = 12.3, <1 Hz,
H-60b), 2.03, 2.01, 1.97 (3 ꢁ 3H, 3s, OCOCH3), 1.60 (3H, s,
4.2.21. 4-Acetoxymethyl-1-(20,30,40,60-tetra-O-acetyl-b-
D-
galactopyranosyl)-1,2,3-triazole (18b)
From 11 (0.1 g, 0.27 mmol), propargyl acetate (27
lL,
0.27 mmol) and C3H7COOCu(PPh3)2 (1.8 mg, 2.7 mol) according
l

É. Bokor et al. / Carbohydrate Research 351 (2012) 42–48
47
to Section 4.2. Purified by column chromatography (1:1 EtOAc–
hexane) to yield 0.12 g (92%) of white solid. Mp: 110–112 °C;
5.32 (1H, dd, J = 9.9, 2.5 Hz, H-30), 5.25, 5.20 (2 ꢁ 1H, 2d,
J = 12.9 Hz in each, CH2a, CH2b), 4.20 (1H, q, J = 6.2 Hz, H-50),
2.26, 2.09, 2.02, 1.89 (4 ꢁ 3H, 4s, OCOCH3), 1.28 (3H, d, J = 6.2 Hz,
CH3); 13C NMR (CDCl3): d (ppm) 170.4, 170.1, 169.5, 168.8
(OCOCH3), 143.0 (triazole C-4), 122.0 (triazole C-5), 85.9 (C-10),
72.3, 70.8, 69.6, 67.8 (C-20–C-50), 57.1 (CH2), 20.5, 20.3, 20.2, 19.9
(OCOCH3), 15.7 (CH3). Anal. Calcd for C17H23N3O9 (413.38): C,
49.39; H, 5.61; N, 10.17. Found: C, 49.32; H, 5.75; N, 10.11.
[
a
]
D ꢀ7 (c 0.50, CHCl3); 1H NMR (CDCl3): d (ppm) 7.93 (1H, s, tria-
zole CH), 5.92 (1H, d, J = 9.2 Hz, H-10), 5.57–5.52 (2H, m, H-20, H-40),
5.33–5.19 (3H, m, H-30, CH2), 4.32 (1H, pseudo t, J = 6.2, 6.2, H-50),
4.25–4.13 (2H, m, H-60a, H-60b), 2.24, 2.10, 2.05, 2.02, 1.89 (5 ꢁ 3H,
5s, OCOCH3); 13C NMR (CDCl3): d (ppm) 170.6, 170.1, 169.8, 169.6,
168.8 (OCOCH3), 143.3 (triazole C-4), 122.1 (triazole C-5), 85.9 (C-
10), 73.8, 70.5, 67.7, 66.7 (C-20–C-50), 61.1 (C-60), 57.2 (CH2), 20.6,
20.4 (2), 20.3, 20.0 (OCOCH3). Anal. Calcd for C19H25N3O11
(471.42): C, 48.41; H, 5.35; N, 8.91. Found: C, 48.52; H, 5.26; N,
8.78.
4.2.26. 4-Phenyl-1-(20,30,40-tri-O-acetyl-b-
L-fucopyranosyl)-1,2,3-
triazole (20d)
From 13 (0.1 g, 0.32 mmol), phenylacetylene (35
and C3H7COOCu(PPh3)2 (10.7 mg, 16 mol) according to Sec-
tion 4.2. Purified by column chromatography (2:3 EtOAc–hexane)
to yield 0.13 g (97%) of white solid. Mp: 237–239 °C; [ +67 (c
lL, 0.32 mmol)
l
4.2.22. 4-Phenyl-1-(20,30,40,60-tetra-O-acetyl-b-
D-
galactopyranosyl)-1,2,3-triazole (18d)
a]
D
From 11 (0.1 g, 0.27 mmol), phenylacetylene (29
l
L, 0.27 mmol)
0.51, CHCl3); 1H NMR (CDCl3): d (ppm) 8.08 (1H, s, triazole CH),
7.87–7.29 (5H, m, aromatics), 5.89 (1H, d, J = 9.2 Hz, H-10), 5.62
(1H, pseudo t, J = 9.9, 9.9 Hz, H-20), 5.42 (1H, d, J = 2.5 Hz, H-40),
5.29 (1H, dd, J = 9.9, 2.5 Hz, H-30), 4.16 (1H, q, J = 6.2 Hz, H-50),
2.26, 2.02, 1.89 (3 ꢁ 3H, 3s, OCOCH3), 1.28 (3H, d, J = 6.2 Hz,
CH3); 13C NMR (CDCl3): d (ppm) 170.2, 169.7, 169.1 (OCOCH3),
148.1 (triazole C-4), 130.0, 128.7 (2), 128.3, 125.8 (2) (aromatics),
117.7 (triazole C-5), 86.2 (C-10), 72.6, 71.1, 69.8, 67.8 (C-20–C-50),
20.6, 20.4, 20.2 (OCOCH3), 15.9 (CH3). Anal. Calcd for C20H23N3O7
(417.41): C, 57.55; H, 5.55; N, 10.07. Found: C, 57.64; H, 5.69; N,
9.98.
and C3H7COOCu(PPh3)2 (3.6 mg, 5.4 mol) according to Section 4.2.
l
Purified by column chromatography (4:5 EtOAc–hexane) to yield
0.12 g (90%) of white solid. Mp: 197–199 °C (lit.19 mp: 197–
199 °C); [
a]
D ꢀ44 (c 0.50, CHCl3); 1H and 13C NMR data correspond
to the reported spectra.19
4.2.23. 4-Acetoxymethyl-1-(20,30,40-tri-O-acetyl-
a-L-
arabinopyranosyl)-1,2,3-triazole (19b)
From 12 (0.1 g, 0.33 mmol), propargyl acetate (33
lL,
0.33 mmol) and C3H7COOCu(PPh3)2 (2.2 mg, 3.3 mol) according
l
to Section 4.2. Purified by column chromatography (1:1 EtOAc–
hexane) to yield 0.13 g (96%) of white solid. Mp: 183–184 °C;
Acknowledgements
[a]
+2 (c 0.50, CHCl3); 1H NMR (CDCl3): d (ppm) 7.93 (1H, s, tria-
D
zole CH), 5.81 (1H, d, J = 9.2 Hz, H-10), 5.58 (1H, pseudo t, J = 9.9,
9.2 Hz, H-20), 5.45 (1H, br s, H-40), 5.29 (1H, dd, J = 9.9, 3.1 Hz, H-
30), 5.21, 5.19 (2 ꢁ 1H, 2d, J = 12.9 Hz in each, CH2a, CH2b),
4.20(1H, d, J = 13.6 Hz, H-50a), 4.00 (1H, d, J = 13.6 Hz, H-50b),
2.23, 2.09, 2.04, 1.90 (4 ꢁ 3H, 4s, OCOCH3); 13C NMR (CDCl3): d
(ppm) 170.6, 169.9, 169.6, 168.8 (OCOCH3), 143.3 (triazole C-4),
122.1 (triazole C-5), 86.4 (C-10), 70.2, 68.0, 67.5 (C-20–C-40), 67.1
(C-50), 57.2 (CH2), 20.7, 20.6, 20.3, 20.0 (OCOCH3). Anal. Calcd for
This work was supported by the Hungarian Scientific Research
Fund (OTKA CK 77712 and CK 80763) and by the TÁMOP 4.2.1/B-
09/1/KONV-2010–0007 Project co-financed by the European Union
and the European Social Fund.
References
1. Meldal, M.; Tornoe, C. W. Chem. Rev. 2008, 108, 2952–3015.
2. Agalave, S. G.; Maujan, S. R.; Pore, V. S. Chem. Asian J. 2011, 6, 2696–2718.
3. Dedola, S.; Nepogodiev, S. A.; Field, R. A. Org. Biomol. Chem. 2007, 5, 1006–1017.
4. Dondoni, A. Chem. Asian J. 2007, 2, 700–708.
5. Santoyo Gonzalez, F.; Hernandez-Mateo, F. Top. Heterocycl. Chem. 2007, 7, 133–
177.
6. Aragao-Leoneti, V.; Campo, V. L.; Gomes, A. S.; Field, R. A.; Carvalho, I.
Tetrahedron 2010, 66, 9475–9492.
7. Akula, R. A.; Temelkoff, D. P.; Artis, N. D.; Norris, P. Heterocycles 2004, 63, 2719–
2725.
8. Wilkinson, B. L.; Bornaghi, L. F.; Poulsen, S.-A.; Houston, T. A. Tetrahedron 2006,
62, 8115–8125.
9. Kuberan, B.; Ethirajan, M.; Victor, X. V.; Tran, V.; Nguyen, K.; Do, A.
Chembiochem 2008, 9, 198–200.
10. Carvalho, I.; Andrade, P.; Campo, V. L.; Guedes, P. M. M.; Sesti-Costa, R.; Silva, J.
S.; Schenkman, S.; Dedola, S.; Hill, L.; Rejzek, M.; Nepogodiev, S. A.; Field, R. A.
Bioorg. Med. Chem. 2010, 18, 2412–2427.
11. Dedola, S.; Hughes, D. L.; Nepogodiev, S. A.; Rejzek, M.; Field, R. A. Carbohydr.
Res. 2010, 345, 1123–1134.
12. Li, T. H.; Guo, L. N.; Zhang, Y.; Wang, J. J.; Li, Z. H.; Lin, L.; Zhang, Z. X.; Li, L.; Lin,
J. P.; Zhao, W.; Li, J.; Wang, P. G. Carbohydr. Res. 2011, 346, 1083–1092.
13. Paul, K. J. V.; Loganathan, D. Tetrahedron Lett. 2008, 49, 6356–6359.
14. Kuijpers, B. H. M.; Groothuys, S.; Keereweer, A. B. R.; Quaedflieg, P. J. L. M.;
Blaauw, R. H.; Delft, F. L. v.; Rutjes, F. P. J. T. Org. Lett. 2004, 6, 3123–3126.
15. dos Anjos, J. V.; Sinou, D.; de Melo, S. J.; Srivastava, R. M. Synthesis 2007, 2647–
2652.
16. Chittaboina, S.; Xie, F.; Wang, Q. Tetrahedron Lett. 2005, 46, 2331–2336.
17. Ermolat’ev, D.; Dehaen, W.; Van der Eycken, E. QSAR Comb. Sci. 2004, 23, 915–
918.
18. Baron, A.; Bleriot, Y.; Sollogoub, M.; Vauzeilles, B. Org. Biomol. Chem. 2008, 6,
1898–1901.
19. Rossi, L. L.; Basu, A. Bioorg. Med. Chem. Lett. 2005, 15, 3596–3599.
20. Groothuys, S.; Kuijpers, B. H. M.; Quaedflieg, P. J. L. M.; Roelen, H. C. P. F.;
Wiertz, R. W.; Blaauw, R. H.; Delft, F. L. v.; Rutjes, F. P. J. T. Synthesis 2006,
3146–3152.
C16H21N3O9 (399.35): C, 48.12; H, 5.30; N, 10.52. Found: C, 48.17;
H, 5.46; N, 10.41.
4.2.24. 4-Phenyl-1-(20,30,40-tri-O-acetyl-
a-L-arabinopyranosyl)-
1,2,3-triazole (19d)
From 12 (0.1 g, 0.33 mmol), phenylacetylene (37
and C3H7COOCu(PPh3)2 (2.2 mg, 3.3 mol) according to Section 4.2.
Purified by column chromatography (2:3 EtOAc–hexane) to yield
0.13 g (98%) of white solid. Mp: 217–219 °C; [
lL, 0.33 mmol)
l
a]
D
ꢀ55 (c 0.51,
CHCl3); 1H NMR (CDCl3): d (ppm) 8.07 (1H, s, triazole CH), 7.87–
7.33 (5H, m, aromatics), 5.83 (1H, d, J = 9.2 Hz, H-10), 5.68 (1H,
pseudo t, J = 9.9, 9.2 Hz, H-20), 5.47 (1H, br s, H-40), 5.29 (1H, dd,
J = 9.9, 2.5 Hz, H-30), 4.20 (1H, d, J = 13.6 Hz, H-50a), 3.99 (1H, d,
J = 13.6 Hz, H-50b), 2.24, 2.04, 1.90 (3 ꢁ 3H, 3s, OCOCH3); 13C
NMR (CDCl3): d (ppm) 170.0, 169.8, 169.1 (OCOCH3), 148.2 (tria-
zole C-4), 130.0, 128.8 (2), 128.4, 125.8 (2) (aromatics), 117.7 (tri-
azole C-5), 86.6 (C-10), 70.5, 68.0, 67.7 (C-20–C-40), 67.2 (C-50), 20.9,
20.5, 20.2 (OCOCH3). Anal. Calcd for C19H21N3O7 (403.39): C, 56.57;
H, 5.25; N, 10.42. Found: C, 56.64; H, 5.11; N, 10.27.
4.2.25. 4-Acetoxymethyl-1-(20,30,40-tri-O-acetyl-b-
L-
fucopyranosyl)-1,2,3-triazole (20b)
From 13 (0.1 g, 0.32 mmol), propargyl acetate (32
lL,
0.32 mmol) and C3H7COOCu(PPh3)2 (4.3 mg, 6.4ꢂ
l
mol) according
to Section 4.2. Purified by column chromatography (1:1 EtOAc–
hexane) to yield 0.13 g (96%) of colourless oil. Rf: 0.37 (1:1
21. Pietrzik, N.; Schips, C.; Ziegler, T. Synthesis 2008, 519–526.
22. Nepogodiev, S. A.; Dedola, S.; Marmuse, L.; Oliveira, M. T. d.; Field, R. A.
Carbohydr. Res. 2007, 342, 529–540.
EtOAc–hexane); [
a]
+13 (c 0.52, CHCl3); 1H NMR (CDCl3): d
D
(ppm) 7.94 (1H, s, triazole CH), 5.89 (1H, d, J = 9.2 Hz, H-10), 5.52
(1H, pseudo t, J = 9.9, 9.9 Hz, H-20), 5.42 (1H, d, J = 2.5 Hz, H-40),
23. Lal, S.; Diez-Gonzalez, S. J. Org. Chem. 2011, 76, 2367–2373.

48
É. Bokor et al. / Carbohydrate Research 351 (2012) 42–48
24. Bokor, É.; Docsa, T.; Gergely, P.; Somsák, L. Bioorg. Med. Chem. 2010, 18, 1171–
1180.
28. Angell, Y. L.; Burgess, K. Chem. Soc. Rev. 2007, 36, 1674–1689.
29. Gonda, Z.; Novák, Z. Dalton Trans. 2010, 39, 726–729.
25. Chrysina, E. D.; Bokor, É.; Alexacou, K.-M.; Charavgi, M.-D.; Oikonomakos, G.
N.; Zographos, S. E.; Leonidas, D. D.; Oikonomakos, N. G.; Somsák, L.
Tetrahedron: Asymmetry 2009, 20, 733–740.
26. Horne, W. S.; Yadav, M. K.; Stout, C. D.; Ghadiri, M. R. J. Am. Chem. Soc. 2004,
126, 15366–15367.
30. Gangjee, A.; Yu, J. M.; Kisliuk, R. L. J. Heterocycl. Chem. 2002, 39, 833–840.
31. Szilágyi, L.; Györgydeák, Z. Carbohydr. Res. 1985, 143, 21–41.
32. Czifrák, K.; Kovács, L.; Kövér, K. E.; Somsák, L. Carbohydr. Res. 2005, 340, 2328–
2334.
33. Paulsen, H.; Györgydeák, Z.; Friedmann, M. Chem. Ber. 1974, 107, 1568–1578.
34. Györgydeák, Z.; Thiem, J. Adv. Carbohydr. Chem. Biochem. 2006, 60, 103–182.
35. Györgydeák, Z.; Szilágyi, L. Liebigs Ann. 1987, 235–241.
27. Appendino, G.; Bacchiega, S.; Minassi, A.; Cascio, M. G.; De Petrocellis, L.; Di
Marzo, V. Angew. Chem., Int. Ed. 2007, 46, 9312–9315.