Application of click chemistry towards an efficient synthesis of 1,2,3-1H-triazolyl glycohybrids as enzyme inhibitors

Article abstract of DOI:10.1016/j.carres.2010.10.017

An efficient synthesis of novel 1,2,3-1H-triazolyl glycohybrids with two or more than two sugar units or a chromenone moiety via copper-catalysed azide-alkyne cycloaddition (CuAAC), a 1,3-dipolar cycloaddition of glycosyl azides to 2,3-unsaturated alkynyl glycosides or propargyloxy coumarins is described. The synthesised glycohybrids were screened for their α-glucosidase, glycogen phosphorylase and glucose-6-phosphatase inhibitory activities. A few of the glycohybrids showed promising inhibitory activities against these enzymes.

Full text of DOI:10.1016/j.carres.2010.10.017

Carbohydrate Research 346 (2011) 16–25
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Application of click chemistry towards an efficient synthesis
of 1,2,3-1H-triazolyl glycohybrids as enzyme inhibitors
Namarata Anand a, Natasha Jaiswal b, Sarvesh Kumar Pandey a, A. K. Srivastava b, Rama P. Tripathi a,
⇑
a Medicinal and Process Chemistry Division, Central Drug Research Institute (CSIR), Lucknow 226 001, India
b Biochemistry Division, Central Drug Research Institute (CSIR), Lucknow 226 001, India
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient synthesis of novel 1,2,3-1H-triazolyl glycohybrids with two or more than two sugar units or a
chromenone moiety via copper-catalysed azide–alkyne cycloaddition (CuAAC), a 1,3-dipolar cycloaddi-
tion of glycosyl azides to 2,3-unsaturated alkynyl glycosides or propargyloxy coumarins is described.
Received 1 September 2010
Received in revised form 13 October 2010
Accepted 21 October 2010
Available online 26 October 2010
The synthesised glycohybrids were screened for their
a-glucosidase, glycogen phosphorylase and glu-
cose-6-phosphatase inhibitory activities. A few of the glycohybrids showed promising inhibitory activi-
ties against these enzymes.
Keywords:
Ó 2010 Elsevier Ltd. All rights reserved.
Click chemistry
CuAAC
Glycosyl triazoles
a-Glucosidase
Glucose-6-phosphatase
Glycogen phosphorylase
1. Introduction
tions.26,27 The hydrogen bonding in these compounds can be favour-
able in the binding of biomolecular targets and in enhancing their
Carbohydrates, a group of prominent biomolecules from renew-
able resources that have great structural diversity are crucial com-
ponents at the interface of chemistry and biology. They are
intricately involved in molecular recognition and act as signalling
molecules.1 Most of the intra- and intercellular events are mediated
by different glycoconjugates in all living organisms.2 Therefore, they
are implicated in different ways in the aetiology and pathogenesis of
metabolic disorders, parasitic and other infectious diseases.3–6 Con-
sequently, multivalent glycohybrids with heterocyclic appendages
are of great significance in drug design and development.7,8 The mul-
tivalent nature of these molecules is frequently used to increase the
affinities9,10 to the targets in different biological processes, such as
the binding of bacteria,11–13 bacterial toxins,14,15 galectins16,17 and
other lectins.18,19 Since the introduction of ‘click chemistry’ by K.
Barry Sharpless and Morten Meldal’s group, tremendous work on
improvements of the Huisgen cycloaddition has been reported in
the literature under different reaction conditions to access 1,2,3-
1H-triazoles.20–23 This reaction has extensively been utilised in drug
discovery and the development of several bioconjugates. The medic-
inal importance of these triazoles is due to their bioisosterism with
peptide bonds,24,25 as they can actively participate in hydrogen
bonding, and due to their strong dipole moments, the triazoles are
extremely stable to hydrolysis and oxidative/reductive condi-
solubilities.28 The triazole unit is an important pharmacophore in
several antiviral,29,30 antifungal,31 antibacterial,32,33 antiparasitic34
and antitubercular35 agents. Very recently, glycosyl 1,2,3-1H-
triazoles have been reported to posses
a-glucosidase inhibitory
activity,36–38 which is important in development of new antidiabetic
agents. The glycosyl triazoles also act as inhibitors of galectins-1 and
-3, which are important in the development of anti-HIV and antican-
cer agents.39 In our continued efforts40,41 to develop new chemo-
therapeutics from triazoles we were interested to synthesise
glycosyl triazoles with two different sugar moieties (pyranose/
furanose or saturated/unsaturated) or other oxygen heterocycles
and study their biological activities. Herein, we have reported the
synthesis of glycohybrids consisting of a 1,2,3-1H-triazole unit,
one or two sugar unit(s) and coumarins, using a well-known cop-
per-catalysed azide–alkyne cycloaddition (CuAAC) reaction of two
sugar azides and different alkynes. The compounds prepared were
also screened for their
a-glucosidase, glucose-6-phosphatase and
glycogen phosphorylase inhibitory activities in vitro.
2. Results and discussion
2.1. Syntheses
2.1.1. Synthesis of 2,3-unsaturated alkynyl glycosides
The starting alkynyl glycosides 7–11 were prepared by reaction
⇑
Corresponding author. Tel.: +91 0522 2612411; fax: +91 522 2623405, +91 522
2623938, +91 522 2629504.
of 3,4,6-tri-O-acetyl-D-glucal (1) with different alkynyl alcohols 2–
6 (Scheme 1) as nucleophiles in the presence of a catalytic amount
E-mail address: rpt.cdri@gmail.com (R.P. Tripathi).
0008-6215/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2010.10.017

N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
17
OAc
OAc
O
O
K10, CH2Cl2, r.t.
AcO
X
R
AcO
AcO
+
O
X
HO
2-6
7-11
1
R
2. X = CH2, R = H
3. X = CH2CH2, R = H
7
. X = CH2, R = H
8. X = (CH2)2, R = H
4
. X = -CH(CH2)4CH3, R = H
5. X = (CH2)2, R = (CH2)2CH3
6.
9. X = -CH(CH2)4CH3, R = H
10. X = (CH2)2, R = (CH2)2CH3
X = CH2, R = CH2OH
OAc
O
11. X = CH2, R =
AcO
O
CH2
Scheme 1. Synthesis of 2,3-unsaturated alkynyl glycosides.
of a solid Lewis acid (Montmorillonite K-10, 30 mol %).42 The struc-
tures of these alkynyl glycosides 7 and 8 were established on the
basis of their spectroscopic data as reported in the literature. How-
ever, alkynyl glycosides 9, 10 and 11 were prepared and character-
ised by us for the first time. The structures were in accordance with
their spectroscopic data and microanalysis. It is important to men-
tion here that all the alkynyl glycosides obtained above were pre-
t-BuOH–H2O in presence of CuSO4 and sodium ascorbate at ambient
temperature led to the formation of only one product, 1-(5-deoxy-
1,2-O-isopropylidene-
a-D-xylofuranos-5-yl)-4-(4,6-di-O-acetyl-2,
3-dideoxy- -erythro-hex-2-enopyranos-1-yloxymethyl)-1,2,3-
a
-D
1H-triazole (14) regioselectively in 75% yield (Scheme 2). The regio-
isomeric nature of the compound 14 was established on the basis of
earlier reports35 and its spectroscopic data. The ESIMS of compound
14 displayed m/z 484 corresponding to [M+H]+. In the 1H spectrum
the anomeric proton of the furanose sugar (H-1) appeared at d
5.95 (d, J 3.6 Hz, 1H), while that of the unsaturated pyranose sugar
(H-10) was seen as singlet at d 5.13. A multiplet at d 4.89–4.66 ac-
counted for H-2 and H-4 of the furanose sugar. Three protons, H-5
and H-3 of the xylofuranosyl sugar, were observed as a multiplet
in the range of d 4.01–4.29. The olefinic protons (H-20 and H-30) of
the pyranose sugar were visible as a multiplet in the range of d
5.83–5.86, while H-40 was observed at d 5.33 as a multiplet. The
two methylene protons (H-60) of the unsaturated pyranose sugar,
two protons of the OCH2 linker and two protons (H-2 and H-4) of
the xylofuranose sugar moiety were visible as two multiplets at d
4.38–4.60 and d 4.65–4.90, respectively. The triazolyl ring proton
was visible as a singlet at d 7.72. In the 13C NMR spectrum the
carbonyl carbons of the sugar acetyl groups were seen at d 170.64
dominantly in the
a-anomeric form accompanied by minute
quantity of b anomers. However, only the pure
a
anomers, isolated
by column chromatography, were used in subsequent cycloaddi-
tion reactions.
2.1.2. Synthesis of
azides
a
-
D
-xylofuranosyl and b-
D-glucopyranosyl
5-Azido-5-deoxy-
yl-b-
and
D
-xylofuranose (12)35 and 3,4,6-tetra-O-acet-
D
-glucopyranosyl azide (13)43,44 were prepared from
D-xylose
D
-glucose as reported earlier.
2.1.3. Reaction of
azides with alkynyl glycosides
Reaction of the propynyl glycoside 7 with 5-azido-5-deoxy-1,
a-D-xylofuranosyl and b-D-glucopyranosyl
2-O-isopropylidene-
a-
D-xylofuranose (12) in a mixture of 1:1
OAc
O
O
N3
OAc
O
O
AcO
AcO
N3
HO
CMe2
O
AcO
OAc
13
12
CuSO4 (2 mol %) / sodium
ascorbate (5 mol %) /
O
CuSO4 (2 mol %)/ sodium
ascorbate (5 mol %) /
X
1:1 tert-BuOH--H2O, 30 °C
1:1 tert-BuOH--H2O, 30 °C
OR1
O
R1O
OR1
OR1
OR1
R1O
N
R1O
N
O
N
N
N
O
N
O
X
O
R1O
O
X
O
HO
CMe2
O
16 19, 20
,
,
14, 17, 18
or
or
21, 24, 25,
15, 22, 23
Scheme 2. Preparation of glycohybrid triazoles with terminal alkynyl glycosides and glycosyl azides.

18
N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
and 169.94, while the anomeric C-1 and C-10 of the furanose and
pyranose sugars were observed at d 105.15 and 93.78, respectively.
The olefinic carbons (C-20 and C-30) of the pyranose sugar were
visible at d 127.41 and 124.20, respectively, besides the other usual
signals of both the sugars. The 1,4-regioisomeric nature of the sub-
stituents in the triazole ring was evidenced by chemical shifts of
C-4 and C-5 at d 144.34 and 129.59 in accordance with the earlier
reports.35 Deacetylation of the acetyl group in compound 14 with
NaOMe–MeOH at ambient temperature led to the formation of the
respective deacetylated compound 15 in good yield. The structure
of compound 15 was in full agreement with its spectroscopic data
and microanalysis.
The 1,4-regioisomeric nature of addition product, as recently re-
ported by Micouin0s group,45 may be due to a six-membered polar
transition state (Fig. 1) formed by the complexation of azides and
alkynes with a Cu ligand. Almost similar observations of 1,4-
regioisomeric products during the cycloaddition of azides with
acetylenes have been reported in the literature by several other
groups.35,46,47
were in full agreement with their spectroscopic data and microa-
nalyses (Scheme 3).
2.1.5. Cycloaddition of propargyloxy coumarins 34 and 35 with
sugar azides 12 and 13
The versatility of the method was further explored by the reac-
tion of 7-O-propargyl-4-methyl coumarin (34)51 and 4-O-propar-
gyl coumarin (35)52 with the above two glycosyl triazoles 12 and
13. The propargyloxy coumarins 34 and 35 were prepared by reac-
tion of 7-hydroxy-4-methyl coumarin (32) and 4-hydroxy couma-
rin (33) with propargyl bromide, respectively, in acetone in
presence of anhydrous K2CO3 and tetrabutylammonium bromide
(20 mol % as a catalyst) for 4–5 h at ambient temperature. The ear-
lier methods51,52 for preparation of these propargyloxy coumarins
required a higher reaction temperature and a long reaction time
(>12 h) with comparatively lesser yield as compared to our meth-
od. Cycloaddition of the above 7-O-propargyloxy coumarin 34 and
the above glycosyl azides 12 and 13 separately led to the formation
of the respective glycosyl triazoles 36 and 39 in very good yields,
again with 1,4-regioselectivity. The deacetylation of the acetyl
group in compound 36 with NaOMe–MeOH gave the respective
compound 38 (Scheme 4) in good yields. Similarly, the above prop-
argyloxy coumarin 35 on cycloaddition with the above glycosyl
azides 12 and 13 led to the formation of respective glycohybrid
triazoles53 37 and 40 in very good yields (Scheme 4). The struc-
tures of all the products were established on the basis of their
spectroscopic data and microanalyses.
Having established the reaction conditions for the regioselec-
tive cycloaddition of the above terminal alkyne 7 and the xylofur-
anosyl azide 12, the scope of different substrates in such a
cycloaddition was explored. Thus cycloaddition of the above alky-
nyl glycoside 7 with tetra-O-acetyl-b-D-glucopyranosyl azide (13)
as above in the presence of CuSO4 and sodium ascorbate led to
the formation of the glycosylated triazole 16 in 76% yield. Simi-
larly, the other two terminal alkynyl-2,3-unsaturated glycopyrano-
sides 8 and 9 on CuAAC reaction48,49 with the above glycosyl azides
12 and 13 separately led to the formation of the respective glycos-
ylated triazoles 17, 18, 19 and 20, respectively, in very good yields
(Scheme 2). Deacetylation of the acetyl groups in the above com-
pounds 16, 17, 18, 19 and 20 with NaOMe–MeOH as usual gave
the respective glycohybrids 21, 22, 23, 24 and 25 in good yields
(Scheme 2, Table 1). The structures of all the compounds were in
agreement with their spectroscopic data and microanalyses.
2.2. Biology
The above glycohybrid triazoles were screened for their en-
zyme inhibitory activities against a-glucosidase (EC 3.2.1.20), gly-
cogen phosphorylase (EC 2.4.1.1) and glucose-6-phosphate (EC
3.1.3.9), enzymes that are crucial in the development of diabetes.
The
a
-glucosidase was isolated and purified from rat intestines54
while glycogen phosphorylase55 and glucose-6-phosphatase56,57
were isolated and purified from rat liver following earlier proto-
cols. Among all the compounds screened, compounds 15, 37, 38
and 40, respectively showed 25.9%, 31.4%, 25.9% and 29.6%
2.1.4. Cycloaddition reaction of internal alkynyl glycosides with
glycosyl azides
The cycloaddition of the internal alkynes 10 and 11 with the
glycosyl azides 12 and 13 under the above-mentioned reaction
conditions proved to be futile. Therefore, an alternative method
of thermal cycloaddition as reported in the literature for the cyclo-
addition of internal alkynes with azides was employed.50 Thus,
reaction of the internal alkyne 10 with the above two glycosyl
azides 12 and 13 separately in refluxing toluene led to the forma-
tion of the respective glycosyl triazoles 26 and 27 as almost 1:1
regioisomeric mixture as evidenced by the NMR spectra of the
compounds. However, reaction of the alkyne 11 having similar
substituents on reaction with the above glycosyl azides 12 and
13 led to the formation of respective triglycosylated triazoles 28
and 29, respectively, in good yields (Scheme 3). Deacetylation of
the acetyl groups in the compounds 28 and 29 with NaOMe–MeOH
at ambient temperature gave the respective deacetylated products
30 and 31 in good yields. Structures of all the above compounds
a-glucosidase inhibitory activity at 100
lmol. The standard drug,
acarbose, exhibited 60% inhibition at 100
lmol concentration. On
the other hand compounds 15, 23, 25 and 38 showed 18.5%,
47.7%, 34.1% and 20.0% inhibition of glycogen phosphorylase at
100
inhibited the glucose-6-phosphatase enzyme up to the extent of
25% at 100 M concentration as compared to standard drug
lM concentration. However, only two compounds 23 and 38
l
sodium-ortho-vandate exhibiting 36% inhibition at the same con-
centration. Other compounds of the series did not show any signif-
icant inhibition of any of the above three enzymes.
3. Conclusions
In conclusion, we have synthesised novel glycohybrid triazoles
using the well-known CuAAC reaction of alkynyl glycosides and
propargyloxy coumarins with sugar azides in fair to good yields.
The compounds synthesised were evaluated for three enzymes,
a
-glucosidase, glycogen phosphorylase and glucose-6-phosphatase,
suuggaarr
showing moderate to significant inhibition. Further work in the
series to get better compounds that will serve as antidiabetic agents
is underway.
N
N
N
Cu...Ln
4. Experimental
O
sugar
sugar
H
Commercially available reagent grade chemicals were pur-
chased from Sigma–Aldrich Chemical Co. or Spectrochem Pvt. Ltd
Figure 1. Proposed six-membered transition state.

N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
19
Table 1
Preparation of glycohybrid triazoles based on furanose and pyranose sugars
Entry
Substrate
Products
Alkynyl glycosides
Sugar azides
OR1
N
O
N
O
N
R1O
O
CMe2
O
1
7
12
O
HO
R1 = Ac
4.
1
NaOMe/MeOH
NaOMe/MeOH
1
15.
R = H
OR1
O
N
O
O
N
O
N
CMe2
R1O
2
8
12
HO
O
2
17. R1 = Ac
22. R1 = H
OR1
N
N
O
O
N
R1O
O
O
HO
(CH2)4CH3
CMe2
R1 = Ac
3
9
12
O
8.
1
NaOMe/MeOH
NaOMe/MeOH
R1 = H
23.
OR1
OR1
O
OR1
R1O
R1O
N
N
N
N
N
O
4
7
13
R1O
16. R1 = Ac
O
R1 = H
21.
OR1
O
OR1
OR1
R1O
R1O
N
O
5
6
8
9
13
13
R1O
19. R1 = Ac
O
O
2
NaOMe/MeOH
NaOMe/MeOH
R1 = H
OR1
24.
OR1
OR1
O
R1O
R1O
N
N
20. R1 = Ac
25.
O
N
R1O
R1 = H
(CH2)4CH3
and were used as received. All reactions were followed by TLC on E.
Merck Kieselgel 60 F254, with detection by UV light and/or spray-
ing a 5% H2SO4 in EtOH followed by heating. Column chromatogra-
phy was performed on Silica Gel 60 (60–120 mesh, E. Merck). IR
spectra were recorded as thin films or in chloroform with a Per-
kin–Elmer Spectrum RX-1 (4000–450 cmꢀ1) spectrophotometer.
1H and 13C NMR spectra were recorded on a Brucker DRX-300 in
CDCl3. Chemical shift values are reported in ppm relative to SiMe4
as internal reference, J in Hertz. MS were performed using a Jeol
SX-102 mass spectrometer and ESIMS were performed using a
Quattro II (Micromass) instrument. Elemental analyses were per-
formed on a Perkin–Elmer 2400 II elemental analyzer. Optical rota-
tions were measured in a 1.0-dm tube with a Rudolf Autopol III
polarimeter in CHCl3.
4.1. 3-O-(4,6-Di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranos-1-yl)-oct-1-yne (9)
A solution of tri-O-acetyl-D-glucal (1, 1.0 g, 3.676 mmol) and oc-
tyne-3-ol (0.46 g, 3.676 mmol) in CH2Cl2 (10 mL) was magnetically
stirred in the presence of Montmorillonite K-10 (30 mol %) at
ambient temperature for 1 h. The reaction mixture was filtered
and the filtrate was evaporated under reduced pressure to give a
crude mass. The latter was chromatographed over a SiO2 column
using 1:1 hexane–EtOAc as eluent to give compound 9 as a colour-
less oil. yield (0.98 g, 81%); Rf 0.5 (10:3 hexane–EtOAc); [a] +145
D
(c 0.1, MeOH); IR (Neat) cmꢀ1: 3278, 2934, 1745, 1372, 1026; 1H
NMR (200 MHz, CDCl3 + CCl4): d 0.93 (t, J 6.5 Hz, 3H, –CH2CH3),
1.31–1.52 (m, 6H, 3 ꢁ –CH2), 1.75–1.80 (m, 2H, –CH2), 2.12 (s,

20
N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
OAc
O
N3
O
OAc
O
O
CMe2
AcO
AcO
N3
OAc
HO
12
O
AcO
13
O
X
Toluene/ Reflux
Toluene/ Reflux
10, 11
R
10, R = -CH2CH2CH3
OAc
27a + 27b, 29
26a + 26b, 28
OAc
O
CH2
AcO
O
11
,
R=
O
OAc
O
OAc
OAc
AcO
N
N
O
AcO
N
N
N
O
AcO
O
CMe2
O
N
26a
O
HO
AcO
O
27a
+
+
N
N
OAc
OAc
AcO
N
N
OAc
O
N
N
O
O
OAc
O
AcO
AcO
O
HO
O
CMe2
O
O
27b
26b
AcO
Inseparable regioisomers
Inseparable regioisomers
OR1
O
R1O
R1O
OR1
R1O
R1O
OR1
OR1
N
N
O
R1O
O
OR1
N
N N
O
O
O
O
O
OR1
N
R1O
O
O
HO
O
CMe2
O
28, R1 = Ac
29, R1 = Ac
NaOMe/MeOH
NaOMe/MeOH
30, R1 = H
1
31
, R = H
Scheme 3. Preparation of glycohybrid triazoles with internal alkynyl glycosides and glycosyl azides.
6H, 2 ꢁ –OAc), 2.43 (s, 1H, –C„CH), 4.18 (m, 1H, H-5), 4.19–4.22
(m, 2H, H-6a, –OCH), 4.45 (m, 1H, H-6b), 5.33 (dd, 1H, J3,4 1.5 Hz,
J4,5 8.2 Hz, H-4), 5.39 (s, 1H, H-1), 5.86–5.89 (m, 2H, H-2, H-3);
13C (50 MHz, CDCl3 + CCl4) d 14.08, 20.71, 20.91, 22.5. 25.1, 31.4,
35.5, 62.9, 65.2, 66.09, 67.30, 73.98, 82.31, 91.40, 127.80, 129.28,
169.86, 170.32; ESIMS: m/z 339 (M+H)+; Anal. Calcd for
C18H26O6: C, 63.89; H, 7.74. Found: C, 63.81; H, 7.79.
5.07 (s, 1H, H-1), 5.33 (dd, J3,4 1.1 Hz, J4,5 9.5 Hz, H-4), 5.85–5.97
(m, 2H, H-2, H-3); 13C NMR (50 MHz, CDCl3 + CCl4): d 13.49,
20.20, 20.38, 20.74, 20.86, 22.3, 62.84, 65.24, 66.84, 67.49, 72.75,
94.87, 129.20, 127.69, 169.85, 170.32; ESIMS: m/z 325
(M+H)+; Anal. Calcd for C17H24O6: C, 62.95; H, 7.46. Found:
C, 62.71; H, 7.59.
4.3. 1,4-O-Bis(4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-hex-2-
enopyranos-1-yloxy)-but-2-yne (11)
4.2. 7-O-(4,6-Di-O-acetyl-2,3-dideoxy-
a-
D-erythro-hex-2-
enopyranos-1-yloxy)hept-3-yne (10)
Colourless oil: yield (1 g, 87%); Rf 0.4 (10:4 hexane–EtOAc); [a]
D
Colourless oil: yield (1.0 g, 86%); Rf 0.4 (10:3 hexane–EtOAc);
+311 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3020, 2931, 1743, 1373, 1043;
1H NMR (200 MHz, CDCl3 + CCl4): d 2.12, 2.13, (s, 6H, 2 ꢁ OAc), 4.09
(m, 1H, H-5), 4.22–4.49 (m, 4H, H-6 and OCH2), 5.23 (s, 1H, H-1),
5.30–5.40 (m, 1H, H-4), 5.80–6.00 (m, 2H, H-2, H-3); 13C NMR
[a
]
+212 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3020, 2931, 1743,
D
1373, 1043; 1H NMR (200 MHz, CDCl3 + CCl4): d 0.99 (t, J 7.42 Hz,
3H, –CH3), 1.53 (sixtet,
J 7.1 Hz, 2H, –CH2), 2.10–2.17 (m,
8H, –CH2C„CH, 2 ꢁ –OAc), 2.50 (m, 2H, –CH2), 3.56–3.69 (m, 1H,
(300 MHz, CDCl3 + CCl4):
63.85, 65.24, 92.68, 127.29, 129.75, 169.97, 170.59; ESIMS: m/z
d 20.75, 20.90, 50.88, 55.35, 62.70,
H-5), 3.79–3.92 (m, 1H, H-6a), 4.10–4.30 (m, 3H, H-6b, –OCH2),

N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
21
R1
O
O
R1
O
O
CH2Br
R1 = -OCH2C
34,
CH, R2 =CH3
1
2
35
, R = H, R = -OCH2C
CH
R2
32, 33
K2CO3, TBAB, in acetone
R2
34, 35
32, R1 = OH, R2 = CH3; 33, R1 = H, R2 = OH
CuSO4 (2 mol %) / sodium
ascorbate (5 mol %) /
1:1 tert-BuOH--H2O, 30 °C
OAc
O
O
N3
HO
AcO
N3
O
CMe2
AcO
OAc
13
O
12
R1
R1
O
O
O
O
R2
R2
39, 40
36, 37
N
N
OAc
O
N
N
O
O
N
N
R2 = CH3
N
1
,
AcO
AcO
39, R1 =
R2 = CH3
36,
R =
O
,
O
HO
OAc
CMe2
O
NaOMe, MeOH
N
O
N
O
1
2
40
, R = H, R =
O
HO
CMe2
O
N
OH
N
N
O
R2 = CH3
O
1
,
38
HO
, R =
HO
OH
N
OAc
O
N
N
O
AcO
R2 =
R1 = H,
37,
AcO
OAc
Scheme 4. Preparation of glycohybrid triazoles with sugar and coumarin skeletons.
533 (M+Na)+; Anal. Calcd for C24H32O12: C, 56.24; H, 6.92. Found: C,
56.18; H, 6.98.
sodium ascorbate (0.05 g, 0.2 mmol) in water was added, followed
by addition of a freshly prepared aqueous solution (200 L) of Cu-
l
SO4ꢂ5H2O (0.02 g, 0.09 mmol). This heterogeneous mixture was
stirred vigorously for 6 h at room temperature after which time
the reaction mixture was extracted with EtOAc and water. The
EtOAc layer was dried (anhyd Na2SO4) and evaporated under re-
duced pressure to give a crude product. The latter was purified
by silica gel (60–120 mesh) column chromatography using 1:1
hexane–EtOAc as eluent to give compound 9 as a white solid:
mp 167–168 °C; yield (1.57 g, 75%); Rf 0.5 (3:2 hexane–EtOAc);
4.4. 1-(5-Deoxy-1,2-O-isopropylidene-
a-D-xylofuranos-5-yl)-4-
(4,6-di-O-acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
a-D
yloxymethyl)-1,2,3-1H-triazole (14)
5-Azido-5-deoxy-1,2-O-isopropylidne-
(1.0 g, 4.651 mmol) and propynyl glycoside 7 (1.2 g, 4.651 mmol)
were suspended in a mixture of 1:1 t-BuOH–water (20 mL)
a-D
-xylofuranose
(12)
and stirred magnetically. A freshly prepared solution (500
l
L) of
[a
]
+127.5 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3386, 2926, 1739,
D

22
N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
1375, 766; 1H NMR (200 MHz, CDCl3 + CCl4): d 1.29, 1.43 (s, 6H,
CMe2), 2.07, 2.10 (s, 6H, 2 ꢁ OAc), 3.60 (br s, 1H, –OH), 4.01–4.23
(m, 3H, H-3, H-5), 4.38–4.60 and 4.65–4.90 (m, 6H, OCH2, H-60,
H-2, H-4), 5.14 (s, 1H, H-10), 5.33 (d, J 8.5 Hz, 1H, H-40), 5.83–5.86
(m, 2H, H-20, H-30), 5.95 (d, J 3.6 Hz, 1H, H-1), 7.72 (s, 1H, triazol-
yl-H); 13C NMR (50 MHz, CDCl3 + CCl4): d 20.77, 20.88, 26.23,
26.87, 49.5, 61.25, 62.80, 65.27, 67.09, 74.44, 79.30, 85.40, 93.78,
105.15, 111.85, 124.20, 127.41, 129.59, 144.34, 169.94, 170.64;
ESIMS: m/z 484 (M+H)+; Anal. Calcd for C21H29N3O11: C, 52.17; H,
6.05; N, 8.69. Found: C, 52.01; H, 6.18; N, 8.49.
(M+H)+, 520 (M+Na)+; Anal. Calcd for C22H31N3O11: C, 53.11; H,
6.28; N, 8.45. Found: C, 52.98; H, 6.39; N, 8.34.
4.8. 1-(5-Deoxy-1,2-O-isopropylidene-
(4,6-di-O-acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
yloxyhexyl)-1,2,3-1H-triazole (18)
a-D-xylofuranos-5-yl)-4-
a
-D
Colourless solid: mp 120–122 °C, yield (0.98 g, 76%); Rf 0.4 (49:1
CHCl3–MeOH); [
D +250 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3220, 2940,
a]
1750, 1377, 856; 1H NMR (300 MHz, CDCl3 + CCl4): d 0.80 (m, 3H,
CH3), 1.26, 1.44 (s, 6H, CMe2), 1.30–151 (m, 6H, 3 ꢁ –CH2), 1.78–
1.98 (m, 2H, –CHCH2), 2.16, 2.06 (s, 6H, 2 ꢁ OAc), 4.12–4.30 (m,
5H, H-5, –OCH2CH2, H-50), 4.40–4.65 (m, 3H, H-4, H-6), 4.80 (m,
1H, H-2), 4.90 (m, 1H, –triazolyl-CH–O–), 4.98 (s, 1H, H-10), 5.30
(d, J4,5 9.5 Hz, 1H, H-40), 5.70 (d, J3,2 10.2 Hz, 1H, H-30), 5.88 (d,
1H, J2,3 10.2 Hz, H-20), 5.95 (d, J 3.2 Hz, 1H, H-1), 7.65 (s, 1H, triaz-
olyl H); 13C NMR (50 MHz, CDCl3 + CCl4): d 14.09, 20.75, 20.91,
22.56, 26.23, 26.91, 31.59, 35.89, 49.06, 62.99, 65.30, 67.35,
71.17, 74.43, 77.60, 79.31, 85.39, 91.72, 105.17, 111.85, 122.97,
127.84, 129.13, 148.55, 169.90, 170.46; ESIMS: m/z 576 (M+Na)+;
Anal. Calcd for C26H39N3O11: C, 56.41; H, 7.10; N, 7.59. Found: C,
56.38; H, 7.22; N, 7.48.
4.5. 1-(5-Deoxy-1,2-O-isopropylidene-a-D-xylofuranos-5-yl)-4-
(2,3-dideoxy- -erythro-hex-2-enopyranos-1-yloxymethyl)-
a-D
1,2,3-1H-triazole (15)
Compound 14 (0.50 g, 1.0 mmol) was dissolved in NaOMe solu-
tion in MeOH (3 mL, 1 M) and was kept at room temperature for
30 min. The reaction mixture was neutralised with aq 3 N HCl,
and the solvent was evaporated under reduced pressure. The resi-
due thus obtained was dissolved in MeOH and filtered off. The fil-
trate was concentrated to give compound 15 as a viscous liquid:
yield (0.360 g, 88%); Rf 0.5 (4:1 CHCl3–MeOH); [
a]
+16 (c 0.1,
D
MeOH); IR (Neat) cmꢀ1: 3423, 2369, 1637, 1220, 771; 1H NMR
(300 MHz, CD3OD): d 1.30, 1.42 (s, 6H, CMe2), 3.65–3.90 (m, 3H,
H-3, H-6), 4.07–4.20 (m, 2H, H-5), 4.40–4.90 (m, 6H, H-2, H-4,
H-4, –OCH2, H-40), 5.10 (s, 1H, H-10), 5.72 (m, 1H, H-20), 5.98 (m,
2H, H-1, H-30), 7.94 (s, 1H, triazolyl-H), 13C NMR (50 MHz, CD3OH):
d 26.30, 26.97, 56.24, 61.32, 62.48, 63.97, 73.30, 75.12, 80.20,
86.35, 94.41, 105.99, 112.66, 125.58, 126.32, 134.89, 145.4; ESIMS:
m/z 422 (M+Na)+; Anal. Calcd for C17H25N3O8: C, 51.12; H, 6.31; N,
10.52. Found: C, 50.97; H, 6.52; N, 10.47.
4.9. 1-(2,3,4,6-Tetra-O-acetyl-b-
D-glucopyranose-5-yl)-4-(4,6-di-
O-acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
a-D
yloxyethyl)-1,2,3-1H-triazole (19)
Colourless solid: mp 140–145 °C; yield (1.35 g, 80%); Rf 0.5
(49:2 CHCl3–MeOH); [
a]
+78 (c 0.1, MeOH); IR (KBr) cmꢀ1
:
D
3465, 2365, 1749, 1656, 1373, 768; 1H NMR (300 MHz,
CDCl3 + CCl4): d 1.84, 2.00, 2.09, 2.05, 2.06, 2.07 (s, 18H, 6 ꢁ OAc),
3.03 (m, 2H, –OCH2CH2-triazolyl), 3.75 (m, 1H, H-5), 3.92–4.38
(m, 7H, H-50, H-6, –OCH2, H-60), 4.98 (s, 1H, H-10), 5.12–5.42 (m,
4H, H-2, H-3, H-4, H-40), 5.80–5.93 (m, 3H, H-1, H-20, H-30), 7.61
(s, 1H, triazolyl-H); 13C NMR (50 MHz, CDCl3 + CCl4): d 20.04,
20.43, 20.56, 20.68, 20.86, 26.50, 61.44, 62.80, 67.01, 67.41,
67.67, 70.20, 72.63, 75.10, 76.32, 76.96, 85.64, 94.57, 119.74,
127.67, 129.22, 145.63, 168.55, 169.07, 169.49, 169.84, 170.04,
4.6. 1-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranos-5-yl)-4-(4,6-di-O-
acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
a-D
yloxymethyl)-1,2,3-1H-triazole (16)
White solid: mp 90–100 °C; yield (1.3 g, 76%); Rf 0.5 (49:1
CHCl3–MeOH); [
a
]
ꢀ28 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3465,
170.37; ESIMS m/z 678.1 (M+Na)+; Anal. Calcd for C28H37N3O15
C, 51.30; H, 5.69; N, 6.41. Found: C, 51.26; H, 5.74; N, 6.37.
:
D
2365, 1749, 1656, 1373, 768; 1H NMR (300 MHz, CDCl3 + CCl4): d
1.84, 2.00 (s, 6H, 2 ꢁ –OAc), 2.07–2.05 (s, 12H, 4 ꢁ –OAc), 4.10–
4.04 (m, 3H, H-6, H-50), 4.19 (m, 1H, H-5), 4.32 (m, 2H, H-60),
4.71 (s, 2H, –OCH2), 5.05 (s, 1H, H-10), 5.29 (m, 2H, H-4, H-3),
5.45 (m, 2H, H-40, H-2), 5.95–5.90 (m, 3H, H-1, H-20,H-30), 7.91 (s,
1H, triazolyl-H); 13C NMR (50 MHz, CDCl3 + CCl4): d 20.01, 20.41,
20.51, 20.67, 20.80, 56.18, 57.88, 61.41, 62.70, 65.22, 67.65,
70.42, 72.65, 75.02, 85.61, 94.50, 121.24, 127.44, 129.55, 145.43,
148.6, 168.75, 169.02, 169.50, 169.73, 170.02, 170.32; ESIMS: m/z
642 (M+H)+, 664.2 (M+Na)+; Anal. Calcd for C27H35N3O15: C,
50.55; H, 5.50; N, 6.55. Found: C, 50.51; H, 5.62; N, 6.48.
4.10. 1-(2,3,4,6-Tetra-O-acetyl-b-
O-acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
yloxyhexyl)-1,2,3-1H-triazole (20)
D-glucopyranos-5-yl)-4-(4,6-di-
a-D
Colourless solid: mp 130 °C; yield (1.48 g, 77.8%); Rf 0.4 (49: 1
CHCl3–MeOH); [
+119 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3479,
a
]
D
2938, 1753, 1642, 1220, 660; 1H NMR (300 MHz, CDCl3 + CCl4): d
0.86 (m, 3H, –alkyl-CH3), 1.28 (m, 6H, 3 ꢁ –CH2), 1.84 (m, 5H, –
CHCH2. OAc), 1.99, 2.03, 2.07 (s, 15H, 5 ꢁ OAc), 3.80–4.40 (m, 7H,
H-5, H-50, H-6, –OCH2, H-60), 4.80 (s, 1H, H-10), 4.90 (m, 1H, –triaz-
olyl-CH–O–) 5.12–5.42 (m, 4H, H-2, H-3, H-4, H-40), 5.80–5.93 (m,
3H, H-1, H-20, H-30), 7.61 (s, 1H, triazolyl-H); d 13C NMR (50 MHz,
CDCl3 + CCl4): d 14.04, 19.88, 20.31, 20.37, 20.52, 20.61, 20.81,
22.50, 25.44, 31.60, 36.40, 61.31, 62.95, 65.28, 67.32, 67.66,
70.52, 71.60, 72.31, 75.14, 85.69, 91.61, 119.49, 128.00, 128.83,
150.16, 168.92, 169.22, 169.60, 169.81, 170.04, 170.17; ESIMS:
m/z 678.1 (M+Na)+; Anal. Calcd for C32H45N3O15: C, 54.00; H,
6.37; N, 5.90. Found: C, 53.94: H, 6.43; N, 5.86.
4.7. 1-(5-Deoxy-1,2-O-isopropylidene-
(4,6-di-O-acetyl-2,3-dideoxy-b- -erythro-hex-2-enopyranos-1-
yloxyethyl)-1,2,3-1H-triazole (17)
a-D-xylofuranos-5-yl)-4-
D
White solid: mp 140–145 °C, yield (1.08 g, 78%); Rf 0.5 (4:6 hex-
ane–EtOAc); [
+62 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3424, 2924,
a]
D
1657, 1051, 673; 1H NMR (200 MHz, CDCl3 + CCl4): d 1.29, 1.47 (s,
6H, CMe2), 2.07, 2.12 (s, 6H, 2 ꢁ –OAc), 3.06 (t, J 6.2 Hz, 2H, –triazol-
yl-CH2–), 3.83 (m, 1H, H-3), 3.95–4.31 (m, 5H, H-5,-OCH2CH2, H-50),
4.40–4.61 (m, 3H, H-4, H-60), 4.85 (m, 1H, H-2), 5.05 (s,1H, H-10), 5.29
(dd, J3,4 1.1, J2,3 9.6 Hz, 1H, H-40), 5.87–5.84 (m, 2H, H-20, H-30), 5.99
(d, J 3.5 Hz, 1H, H-1), 7.61 (s, 1H, triazolyl-H); 13C NMR (50 MHz,
CDCl3 + CCl4): d 20.75, 20.91, 26.23, 26.52, 48.69, 62.97, 65.35,
67.02, 67.45, 74.44, 77.60, 79.38, 85.37, 94.52, 105.16, 111.83,
123.17, 127.62, 129.27, 144.94, 169.94, 170.63; ESIMS: m/z 498
4.11. 1-(b-D-Glucopyranos-5-yl)-4-(2,3-dideoxy-b-D-erythro-
hex-2-enopyranos-1-yloxymethyl)-1,2,3-1H-triazole (21)
Viscous oil: yield (0.25 g, 83%); Rf 0.4 (7:3 CHCl3–MeOH); [
a
]
D
+9.6 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3417, 2927, 2366, 1588,
1219, 772; 1H NMR (300 MHz, CDCl3 + CD3OD): d 3.52–4.09 (m,

N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
23
9H, H-3, H-4, H-40, H-5, H-50, H-6, H-60), 4.70 (s, 2H, –OCH2), 5.10 (s,
1H, H-10), 5.60 (d, 1H, J 9.1 Hz, H-30), 5.70 (d, 1H, J 9.1 Hz, H-20),
5.93 (d, J 10.2 Hz, 1H, H-1), 8.03 (s, 1H, triazolyl-H); 13C NMR
(50 MHz, CD3OD) d 61.6, 62.6, 64.2, 70.7, 73.4, 77.1, 78.1, 79.7,
80.9, 89.4, 94.0, 123.2, 124.5, 126.3, 148.9; ESIMS: m/z 391.3
(M+H)+; Anal. Calcd for C15H23N3O9: C, 46.20; H, 5.95; N, 10.79.
Found: C, 46.11; H, 6.01; N, 10.71.
771; 1H NMR (300 MHz, CDCl3 + DMSO-d6): d 0.88 (m, 3H, –al-
kyl-CH3), 1.30 (m, 6H, 3 ꢁ –CH2), 1.78 (m, 2H, –O–(CH)CH2),
3.30–4.15 (m, 12H, H-2, H-3, H-4, H-5, H-6, H-60, 4 ꢁ –OH), 4.81–
4.91 (m, 2H, –O–(CH)–CH2–, H-10), 5.49 (d, 1H, J 9.0 Hz, H-20),
5.60 (m, 1H, H-30), 5.86 (d, J 9.7 Hz, 1H, H-1), 7.98 (s, 1H, triazolyl
H); 13C NMR (50 MHz, CDCl3 + DMSO-d6): d 19.06, 27.29, 30.15,
36.27, 36.46, 40.72, 65.86, 67.28, 74.49, 75.01, 77.19, 77.75, 81.9,
84.99, 92.81, 96.01, 126.32, 130.39, 139.60; 153.19; ESIMS: m/z
482 (M+Na)+; Anal. Calcd for C20H33N3O9: C, 52.28; H, 7.24; N,
9.14. Found: C, 52.19; H, 7.29; N, 9.09.
4.12. 1-(5-Deoxy-1,2-O-isopropylidene-a-D-xylofuranos-5-yl)-4-
(2,3-dideoxy- -erythro-hex-2-enopyranos-1-yloxyethyl)-
a-D
1,2,3-1H-triazole (22)
4.16. 1-(5-Deoxy-2,3-O-isopropylidene-
(4,6-di-O-acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
yloxyethyl)-5-propyl-1,2,3-1H-triazole (26a) and 1-(5-deoxy-
2,3-O-isopropylidene- -xylofuranos-5-yl)-5-(4,6-di-O-acetyl-
2,3-dideoxy- -erythro-hex-2-enopyranos-1-yloxyethyl)-4-
a-D-xylofuranos-5-yl)-4-
Colourless solid: mp 50–55 °C; yield (0.19 g, 82%); Rf 0.5 (4:1
a-D
CHCl3–MeOH); [
a
]
+11 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3379,
D
2926, 2368, 1658, 1055; 1H NMR (300 MHz, DMSO-d6) d 1.21,
1.33 (s, 6H, CMe2), 2.89 (t, 3H, J 6.6 Hz, –CH2-triazolyl), 3.51 (m,
4H, –OCH2, H-60), 3.90 (m, 2H, H-5), 4.09 (s, 1H, H-3), 4.32–4.60
(m, 4H, H-2, H-4, H-40, H-50), 5.10 (s, 1H, H-10), 5.63 (d, J 9.9 Hz,
1H, H-30), 5.82 (d, J 9.9 Hz, 1H, H-20), 5.86 (d, 1H, J 3.4 Hz, H-1),
7.89 (s, 1H, triazolyl H); 13C NMR (50 MHz, DMSO-d6) d 26.45,
26.52, 27.06, 49.17, 61.25, 62.66, 67.04, 73.26, 73.94, 79.66,
85.44, 94.06, 104.94, 111.17, 123.44, 125.75, 134.97, 144.57;
ESIMS: m/z 414 (M+H)+, 436 (M+Na)+; Anal. Calcd for
a-D
a-D
propyl-1,2,3-1H-triazole (26b) as inseparable regioisomers
Brown viscous: yield (1.15 g, 72% yield); Rf 0.6 (49:1 CHCl3–
MeOH); [
a
]
+42.7 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3423, 2927,
D
2363, 1735, 1219, 672; 1H NMR (300 MHz, CDCl3 + CCl4): because
of the regioisomeric nature duplicity of almost all the signals were
observed. d 0.98, 1.24 (two t merged with each other, J 7.12 Hz, 6H,
regioisomeric CH3CH2CH2–), 1.26 (s, 6H, CH3 of CMe2), 1.44 (s, 6H,
CH3 of CMe2), 1.74–1.67 (m, 2H, –CH2), 1.62, 1.72 (m, each 2H,
CH3CH2–), 2.08, 2.09, 2.13, 2.16 (s, 12H, 2 ꢁ –OAc), 2.63 (m, 4H,
2 ꢁ triazolyl-CH2CH2CH3), 2.93–2.89 (m, 4H, triazolyl-CH2CH2O–),
3.70, 3.90 (m, 4H, H-5), 4.00–4.25 (m, 8H, 2 ꢁ –OCH2CH2–, H-50,
H-3), 4.38–4.27 (m, 4H, 2 ꢁ H-60), 4.50–4.68 (m, 4H, regioisomeric
H-2, H-4), 4.94, 5.00 (s, 1H, 2 ꢁ H-10), 5.23–5.94 (m, 2H, regioiso-
meric H-40), 5.93–5.78 (m, 6H, regioisomeric H-20, H-30, H-1); 13C
NMR (50 MHz, CDCl3 + CCl4): d 13.90, 14.00, 22.44, 22.72, 23.20,
24.14 (–CH3 of acetate), 26.17, 26.82, 26.86, 27.04 (CMe2) regioiso-
meric mix, 29.66, 30.55 (–CH2), 45.84, 46.21 (C-5), 62.60, 62.81
(regioisomeric mix C-60), 65.20, 65.36 (regioisomeric mix C-40),
66.76, 66.86 (–OCH2), 66.98, 67.66 (C-50), 74.22, 74.30 (C-2),
79.62, 79.71 (C-3), 85.23, 94.2, 94.3 (C-10), 105.0 (C-1), 111.65,
111.61 (CMe2) 127.07, 128.76, (regioisomeric C-20), 129.00,
129.50 (regioisomeric C-30), 132.33, 134.9, (regioisomeric triazolyl
C-4), 141.42, 145.0 (regioisomeric triazolyl C-4), 167.41, 169.92,
170.39, 170.60, (regioisomeric –OAc); ESIMS: m/z 562 (M+Na)+;
Anal. Calcd for C25H37N3O10: C, 55.65; H, 6.91; N, 7.79. Found: C,
55.59; H, 6.98; N, 7.66.
C
18H27N3O8: C, 52.29; H, 6.58; N, 10.16. Found: C, 52.21; H, 6.63;
N, 10.05.
4.13. 1-(5-Deoxy-1,2-O-isopropylidene-a-D-xylofuranos-5-yl)-4-
(2,3-dideoxy-a-D-erythro-hex-2-enopyranos-1-yloxyhexyl)-
1,2,3-1H-triazole (23)
Colourless solid: mp 60–65 °C; yield (0.20 g, 84%); Rf 0.6 (4:1
CHCl3–MeOH); [
a
]
+28 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3420,
D
2940, 1658, 1377, 856; 1H NMR (300 MHz, CDCl3 + CD3OD): d
0.89 (m, 3H, –CH3), 1.42 (s, 3H, CH3), 1.31, 1.43 (s, 6H, CMe2),
1.19–1.50 (m, 6H, 3 ꢁ alkyl CH2), 1.77, 1.92 (m, 2H, –CHCH2),
3.65–3.85 (m, 3H, H-50, H-60), 4.02–4.20 (m, 2H, H-5), 4.40–4.78
(m, 4H, H-3, H-4, H-40, and –O–CH-alkyl), 4.85 (s, 1H, H-10), 5.00
(m, 1H, H-2), 5.61 (d, J 10.7 Hz, 1H, H-20), 5.93 (m, 2H, H-1, H-30),
7.83 (s, 1H, triazolyl-H); 13C NMR (50 MHz, CDCl3 + CD3OD): d
17.59, 26.32, 29.24, 29.68, 30.34, 35.37, 39.69, 53.55, 65.44,
65.85, 74.06, 76.26, 78.08, 83.19, 89.31, 95.06, 109.00, 115.69,
127.21, 129.58, 137.69, 152.48. ESIMS m/z 492.2 (M+Na)+; Anal.
Calcd for C22H35N3O8: C, 56.28; H, 7.51; N, 8.95. Found: C, 56.19;
H, 7.62; N, 8.89.
4.17. 1-(2,3,4,6-Tetra-O-acetyl-b-
O-acetyl-2,3-dideoxy- -erythro-hex-2-enopyranos-1-
yloxymethyl)-5-propyl-1,2,3-1H-triazole (27a) and 1-(2,3,4,6-
tetra-O-acetyl-b- -glucopyranos-5-yl)-5-(4,6-di-O-acetyl-2,3-
dideoxy- -erythro-hex-2-enopyranos-1-yloxymethyl)-4-
D-glucopyranos-5-yl)-4-(4,6-di-
4.14. 1-(b-
D
-Glucopyranose-5-yl)-4-(2,3-dideoxy-
a
-
D
-erythro-
a-D
hex-2-enopyranos-1-yloxyethyl)-1,2,3-1H-triazole (24)
D
Colourless gum: yield (0.20 g, 85%); Rf 0.5 (7:3 CHCl3–MeOH);
a-D
[
a
]
+15.6 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3430, 2362, 1588, 765;
propyl-1,2,3-1H-triazole (27b) as inseparable regioisomers
D
1H NMR (300 MHz, CDCl3+ DMSO-d6): d 2.99 (t, 2H, J 6.1 Hz, triaz-
olyl-CH2CH2), 3.20 (br s, 4 ꢁ OH), 3.40–3.62 (m, 8H, H-3, H-4, H-6,
H-5, H-50, 2 ꢁ OH), 3.70–3.90 (m, 5H, H-2, –OCH2, H-60) 4.06 (m,
1H, H-40), 4.95 (s, 1H, H-10), 5.48 (d, J 9.2 Hz, 1H, H-30), 5.63 (m,
1H, H-20), 5.86 (d, J 10.1 Hz, 1H, H-1), 7.93 (s, 1H, triazolyl-H),
Brown viscous oil: yield (1.50 g, 70%); Rf 0.4 (49:1 CHCl3–
MeOH); [
a
]
+25.4 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3021, 2368,
D
1750, 1662, 1220, 765; 1H NMR (200 MHz, CDCl3 + CCl4): d 0.98,
1.03 (two t merged with each other, J 7.12 Hz, 6H, regioisomeric
CH3CH2CH2–), 1.60–1.75 (m, 4H, regioisomeric CH3CH2CH2–),
1.81, 1.82, 2.02, 2.05, 2.06, 2.07 (s, 36H, regioisomeric 6 ꢁ –OAc),
2.50–2.62 (m, 4H, regioisomeric CH3CH2CH2–), 2.85–3.12 (m, 4H,
regioisomeric –OCH2CH2–), 3.60–4.40 (m, 20H, regioisomeric H-3,
H-4, H-5, H-50, H-6, H-60, OCH2CH2-triazolyl), 5.01 (s, 2H, regioiso-
meric H-10), 5.20–5.40 (m, 4H, regioisomeric H-2, H-40), 5.70–5.90
(m, 6H, H-1, H-20, H-30), 13C NMR (50 MHz, CDCl3 + CCl4): d 13.83,
14.00 (regioisomeric alkyl-CH3), 20.09, 20.46, 20.64, 20.88 (OAc)
22.54, 25.85, 26.74 (alkyl-CH2), 61.49 (C-6), 62.79 (C-40), 65.14,
65.26 (regioisomeric C-2), 66.97, 67.20 (regioisomeric C-4 pyra-
nose sugar), 67.64, 67.74 (regioisomeric –OCH2), 69.69 (C-50),
13C NMR (50 MHz, CDCl3 + DMSO-d6):
d 29.75, 31.35, 66.09,
67.55, 71.71, 74.65, 77.27, 77.92, 82.11, 85.10, 92.69, 92.86,
126.54, 130.41, 139.73, 149.17; ESIMS: m/z 426 (M+Na)+; Anal.
Calcd for C16H25N3O9: C, 47.64; H, 6.25; N, 10.42. Found: C,
47.59; H, 6.32; N, 10.36.
4.15. 1-(b-D-Glucopyranos-5-yl)-4-(2,3-dideoxy-a-D-erythro-
hex-2-enopyranos-1-yloxyhexyl)-1,2,3-1H-triazole (25)
Colourless gum: yield (0.14 g, 83%); Rf 0.6 (7:3 CHCl3–MeOH);
[a]
+101 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3430, 2925, 2366, 1584,
D

24
N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
72.89 (C-3), 75.00 (C-5), 84.82, 85.18 (regioisomeric C-1), 94.54,
94.70 (regioisomeric C-10), 127.75, 129.06, 129.66, (C-20, C-30),
142.66, 130.92 (triazolyl C-4, C-5), 168.30, 169.00, 169.86,
170.13, 170.50 (–OAc); ESIMS: 698.2 m/z (M+H)+, 720 (M+Na)+;
Anal. Calcd for C31H43N3O15: C, 53.37; H, 6.21; N, 6.02. Found: C,
53.31; H, 6.28; N, 6.08.
4.21. 1-(b-
D
-Glucopyranose-5-yl)-4-(2,3-dideoxy-
a
-
a
D
-erythro-
-erythro-
hex-2-enopyranos-1-yloxymethyl)-5-(2,3-dideoxy-
hex-2-enopyranos-1-yloxymethyl) 1,2,3-1H-triazole (31)
-D
Light brown gum: yield (0.30 g, 79%); Rf 0.5 (7:3 CHCl3–MeOH);
[a]
+44.6 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3413, 2362, 1650, 1567,
D
1415, 657; 1H NMR (300 MHz, CD3OD): d 3.31 (br s, 1H, OH), 3.56
(m, 1H, H-4), 3.62–3.75 (m, 7H, H-3, H-5, H-50, H-500, H-6), 3.90,
4.09 (m, 2H, H-60, H-600), 4.21–4.29 (m, 2H, H-40, H-400), 4.74–4.79
(m, 5H, H-2, 2 ꢁ –OCH2), 5.07 (s, 2H, H-10, H-100), 5.70–5.76 (m,
3H, H-20, H-200, H-30), 5.75–5.67 (m, 2H, H-1 and H-300);. 13C NMR
(50 MHz, CD3OD): d 52.19, 61.0, 62.44, 62.70, 64.08, 64.19, 71.0,
73.30, 73.76, 78.40, 81.14, 87.80, 87.92, 94.93, 95.16, 97.46,
126.52, 126.73, 135.51, 135.67, 138.04, 143.81; ESIMS: m/z 570
(M+Na)+; Anal. Calcd for C22H33N3O13: C, 48.26, H, 6.08; N, 7.67.
Found: C, 48.16; H, 6.13; N, 7.53.
4.18. 1-(5-Deoxy-1,2-O-isopropylidene- -xylofuranos-5-yl)-
a
-D
4,5-bis-(4,6-di-O-acetyl-2,3-dideoxy- -D-erythro-hex-2-
a
enopyranos-1-yloxymethyl)-1,2,3-1H-triazole (28)
Light brown gum: yield (0.91 g, 64%); Rf 0.5 (49: 2 CHCl3–
MeOH), [
a
]
ꢀ222 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3414, 2926,
D
2361, 1740, 1217, 765; 1H NMR (300 MHz, CDCl3 + CCl4): d 1.27,
1.43 (s, 6H, CMe2), 2.10, 2.13 (s, 12H, 4 ꢁ –OAc), 4.01 (m, 2H, H-
50, H-500), 4.05–4.25 m, 5H, H-3, H-60, H-600), 4.51 (m, 4H, H-4, H-
5, –OH), 4.67–4.73 (m, 5H, 2 ꢁ –OCH2, H-2), 4.84 (s, 1H, H-10),
4.94 (m, 1H, H-40), 5.08 (s, 1H, H-100), 5.28–5.32 (m, 1H, H-400),
5.77 (d, J 10.2 Hz, 1H, H-30), 5.89–5.92 (m, 1H, 2 ꢁ H-20, H-300),
5.94 (d, J 4.8 Hz, 1H, H-1); 13C NMR (50 MHz, CDCl3 + CCl4): d
14.24, 20.75, 20.83, 26.22, 26.92, 46.22, 46.50, 56.65, 56.87,
62.69, 63.17, 64.05, 65.05, 67.55, 74.14, 75.0, 79.35, 79.24, 85.18,
85.36, 93.66, 94.81, 105.07, 111.50, 111.83, 126.55, 130.23,
170.73, 169.85; ESIMS: m/z 748 (M+Na)+; Anal. Calcd for
4.22. 1-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranose-1-yl)-4-(4-
methyl-2H-chromen-2-one-7-yloxymethyl)-1,2,3-1H-triazole
(36)
Colourless solid: mp >250 °C, yield (1.12 g, 73%); Rf 0.5 (49:1
CHCl3–MeOH); [
a
]
D
ꢀ11 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3467,
2365, 1746, 1619, 1378, 857; 1H NMR (300 MHz, CDCl3 + DMSO-
d6): d 1.81, 1.99, 2.01, 2.05 (s, 12H, 4 ꢁ –OAc), 2.41 (s, 3H, coumari-
nyl-CH3), 4.07–4.30 (m, 3H, H-5 and H-6), 5.22 (m, 1H, H-4), 5.26
(s, 3H, –OCH2-triazolyl), 5.48 (dd, J 11.7 Hz, 2.4 Hz, 2H, H-2, H-3,),
6.10 (d, J 11.7 Hz, 1H, H-1), 6.13 (d, J 2.4 Hz, 1H, coumarinyl-H-
3), 6.94 (two d, J 7.5 Hz, 2.4 Hz, 2H, –ArH), 7.51 (d, J 2.4 Hz, 1H,
ArH), 8.08 (s, 1H, triazolyl-H); 13C NMR (50 MHz, CDCl3 + DMSO-
d6) d 23.09, 24.52, 24.98, 25.11, 66.19, 66.71, 72.39, 75.24, 77.31,
79.21, 89.82, 106.84, 116.97, 117.41, 118.66, 127.13, 130.46,
156.93, 160.07, 165.18, 166.02, 173.25, 173.87, 174.27, 174.76;
ESIMS: m/z 610 (M+Na)+; Anal. Calcd for C27H29N3O12: C, 55.20;
H, 4.98; N, 7.15. Found: C, 55.18; H, 5.03; N, 7.11.
C32H43N3O16: C, 52.96; H, 5.97; N, 5.79. Found: C, 52.89; H, 6.03;
N, 5.71.
4.19. 1-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranos-5-yl)-4-(4,6-di-
O-acetyl-2,3-dideoxy-
a-
D-erythro-hex-2-enopyranos-1-
yloxymethyl)-5-(4,6-di-O-acetyl-2,3-dideoxy-
a
-D
-erythro-hex-
2-enopyranos-1-yloxymethyl)-1,2,3-1H-triazole (29)
Colourless gum: yield (1.20 g, 71% yield.); Rf 0.4 (49:1 CHCl3–
MeOH); [
a
]
+54 (c 0.1, MeOH); IR (Neat) cmꢀ1: 3483, 3023,
D
2367, 1749, 1373, 1224, 766; 1H NMR (300 MHz, CDCl3 + CCl4): d
1.85, 2.01, 2.06, 2.07, 2.08, 2.09, 2.11 (s, 24H, 8 ꢁ –OAc), 4.02–
4.13 (m, 4H, H-50, H-500, H-6), 4.15–4.28 (m, 5H, H-5, H-60, H-600),
4.75, 4.83 (s, 4H, 2 ꢁ –OCH2CH2-triazolyl), 4.98–5.06 (m, 2H, H-4,
H-1), 5.17 (s, 1H, H-100), 5.18–5.30 (m, 3H, H-40, H-400, H-3), 5.41
(m, 1H, H-2), 5.81–5.98 (m, 5H, H-1, H-20, H-200, H-30, H-300); 13C
NMR (50 MHz, CDCl3 + CCl4): d 20.10, 20.39, 20.46, 20.50, 20.65,
20.78, 52.33, 55.55, 60.46, 61.21, 61.50, 62.75, 65.22, 67.26,
67.60, 70.00, 70.28, 72.63, 72.82, 75.09, 85.90, 92.24, 93.30,
127.08, 127.30, 129.66, 129.79, 135.65, 143.15, 148.00, 168.75,
168.87, 169.59, 169.71, 169.91, 170.01, 170.40, 170.44; ESIMS:
m/z 884 (M+H)+, 906 (M+Na)+; Anal. Calcd for C38H49N3O21: C,
51.64; H, 5.59; N, 4.75. Found: C, 51.60; H, 5.63; N, 4.71.
4.23. 1-(2,3,4,6-Tetra-O-acetyl-b-D-glucopyranos-1-yl)-4-(2H-
chromen-2-one-4-yloxymethyl) 1,2,3-1H-triazole (37)
Colourless solid: mp >285 °C, yield, (1.24 g, 81%) Rf 0.4 (49:1
CHCl3–MeOH); [
a]
ꢀ32 (c 0.1, DMSO); IR (KBr) cmꢀ1: 3481,
D
3077, 2373, 1750, 1622, 1376, 927; 1H NMR (300 MHz,
CDCl3 + CCl4 + DMSO-d6): d 1.74, 1.93, 1.97, 1.99 (s, 12H, 4 ꢁ –
OAc), 4.02–4.12 (m, 2H, H-6), 4.33 (m, 1H, H-5), 5.17 (t, J 9.7 Hz,
1H, H-4), 5.37 (s, 2H, –OCH2), 5.51 (t, J 9.4 Hz, 1H, H-3), 5.61 (t, J
9.4 Hz, 1H, H-2), 6.00 (s, 1H, H-coumarinyl-H-3), 6.32 (d, J 9.0 Hz,
1H, H-1), 7.28 (m, 2H, –ArH), 7.56 (m, 1H, –ArH), 77.73 (d, J
7.8 Hz, 1H, –Ar H), 8.54 (s, 1H, triazolyl-H), 13C NMR (50 MHz,
4.20. 1-(5-Deoxy-1,2-O-isopropylidene-
(2,3-dideoxy- -erythro-hex-2-enopyranos-1-yloxymethyl)-5-
(2,3-dideoxy- -erythro-hex-2-eno-pyranyloxymethyl)-1,2,3-
1H-triazole (30)
a
-
D
-xylofuranos-5-yl)-4-
CDCl3 + CCl4 + DMSO-d6) d 24.98, 25.36, 25.49, 25.61, 66.79,
a
a
-
-D
D
67.73, 72.71, 75.42, 77.35, 78.62, 89.24, 96.53, 120.37, 121.43,
128.09, 129.04, 129.17, 137.65, 146.91, 158.03, 166.58, 169.40,
173.38, 174.21, 174.42, 174.90; ESIMS: m/z 574 (M+H)+, 596
(M+Na)+; Anal. Calcd for C26H27N3O12: C, 54.45; H, 4.75; N, 7.33.
Found: C, 54.38; H, 4.83; N, 7.29.
Colourless gum; yield (0.25 mg, 80%); Rf 0.5 (4:1 CHCl3–MeOH);
[a
]
D
+20 (c 0.1, MeOH); IR (neat) cmꢀ1: 3409, 2138, 1638, 1413,
771; 1H NMR (300 MHz, DMSO-d6): d 1.20, 1.30 (s, 6H, CMe2),
3.50 (br s, 3H, –OH), 3. 90 (d, J 7.9 Hz, 2H, H-50, H-500), 4.09 (br s,
2H, OH), 4.35–4.45 (m, 2H, H-5), 4.46–4.49 (m, 3H, H-3, H-60, H-
600), 4.51 (s, 4H, 2 ꢁ –OCH2-triazolyl), 4.58–4.62 (m, 2H, H-2, H-
4), 4.69, 4.88 (d, J 12.5 Hz, 2H, H-40, H-400), 5.03 (s, 2H, H-10, H-
100), 5.60 (d, J 10.1 Hz, H-20, H-200), 5.83 (m, 2H, H-300, H-300), 5.86
(d, J 3.7 Hz, 1H, H-1); 13C NMR (50 MHz, CDCl3 + DMSO-d6) d
31.21, 31.86, 52.49, 59.23, 61.29, 67.21, 77.01, 78.19, 78.81,
84.53, 90.21, 98.28, 109.69, 115.89, 129.85, 136.73, 140.45,
151.08; ESIMS: m/z 748 (M+Na)+; Anal. Calcd for C24H35N3O12: C,
51.70; H, 6.33; N, 7.54. Found: C, 51.64; H, 6.39; N, 7.51.
4.24. 1-(b-D-Glucopyranos-1-yl)-4-(4-methyl-2H-chromen-2-
one-7-yloxymethyl)-1,2,3-1H-triazole (38)
Colourless solid: mp >250 °C, yield, (0.32 g, 88%); Rf 0.6 (4:1
CHCl3–MeOH); [
a
]
ꢀ1 (c 0.1, DMSO); IR (KBr) cmꢀ1: 3405, 2364,
D
1692, 1398, 611; 1H NMR (300 MHz, CDCl3 + DMSO-d6): d 2.39 (s,
3H, coumarinyl-4-CH3), 2.74 (m, 1H, H-4), 3.20 (br s, 4 ꢁ OH),
3.51 (m, 3H, H-4, H-6), 3.70 (m, 1H, H-5), 3.81 (t, J 8.7 Hz, 1H, H-
3), 4.02 (m, 1H, H-2), 5.23 (s, 2H, –OCH2), 5.53 (d, J 9.3 Hz, 1H,
H-1), 6.06 (s, 1H, coumarinyl-H), 6.98 (m, 2H, –ArH), 7.56 (d, J
8.6 Hz, 1H, –ArH), 7.86 (m, 2H, ArH), 8.26 (s, 1H, triazolyl-H); 13C

N. Anand et al. / Carbohydrate Research 346 (2011) 16–25
25
9. Mammen, M.; Choi, S. K.; Whitesides, G. M. Angew. Chem., Int. Ed. 1998, 37,
2754–2794.
10. Lee, R. T.; Lee, Y. C. Glycoconjugate J. 2000, 17, 543–551.
11. Lindhorst, T. K.; Dubber, M.; Krallmann-Wenzel, U.; Ehlers, S. Eur. J. Org. Chem.
2000, 2027–2034.
NMR (50 MHz, CDCl3 + DMSO-d6): d 23.39, 45.94, 65.78, 66.73,
74.43, 77.22, 81.98, 82.97, 84.90, 92.79, 106.62, 116.59, 117.56,
118.56, 131.16, 147.00, 159.86, 165.24, 166.17; ESIMS: m/z 442
(M+Na)+; Anal. Calcd for C19H21N3O8: C, 54.41; H, 5.05; N, 10.02.
Found: C, 54.38; H, 5.13; N, 9.96.
12. Nagahori, N.; Lee, R. T.; Nishimura, S. I.; Pagé, D.; Roy, R.; Lee, Y. C.
ChemBioChem 2002, 3, 836–844.
13. Joosten, J. A. F.; Loimaranta, V.; Appeldoorn, C. C. M.; Haataja, S.; Ait El Maate,
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6508.
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Chem. Soc. 2000, 122, 2663–2664.
4.25. 1-(5-Deoxy-2,3-O-isopropylidene-a-D-xylofuranos-5-yl)-4-
(4-methyl-2H-chromen-2-one-7-yloxymethyl)-1,2,3-1H-
triazole (39)
15. Arosio, D.; Vrasidas, I.; Valentini, P.; Liskamp, R. M. J.; Pieters, R. J.; Bernardi, A.
Org. Biomol. Chem. 2004, 2, 2113–2124.
16. Andre, S.; Pieters, R. J.; Vrasidas, I.; Kaltner, H.; Kuwabara, I.; Liu, F. T.; Liskamp,
R. M. J.; Gabius, H. J. ChemBioChem 2001, 2, 822–830.
Colourless solid: yield; mp 145–148 °C; (1.60 g, 80%); Rf 0.5
(49:1 CHCl3–MeOH); [a]
+3 (c 0.1, MeOH); IR (KBr) cmꢀ1: 3326,
D
2927, 2366, 1722, 1622, 1385, 1072, 878; 1H NMR (300 MHz,
CDCl3 + DMSO-d6): d 1.29, 1.42 (s, 6H, CMe2), 2.42 (s, 3H, –CH3),
4.17 (m, 1H, H-3), 4.45–4.59 (m, 3H, H-4, H-5), 4.79 (m, 1H, H-2),
5.25 (s, 2H, –OCH2), 5.95 (d, J 2.9 Hz, 1H, H-1), 6.11 (s, 1H, H-3 cou-
marin), 6.95 (m, 2H, –ArH), 7.48–7.54 (m, 1H, –ArH), 7.95 (s, 1H,
triazolyl H-5); 13C NMR (50 MHz, CDCl3 + DMSO-d6) d 18.48,
26.09, 26.69, 49.29, 74.06, 79.26, 85.31, 95.94, 101.89, 104.94,
111.54, 111.90, 112.43, 113.76, 124.51, 125.60, 152.40, 154.93,
160.77, 161.11; ESIMS: m/z 452 (M+Na)+; Anal. Calcd for
17. Vrasidas, I.; Andre, S.; Valentini, P.; Bock, C.; Lensch, M.; Kaltner, H.; Liskamp, R.
M. J.; Gabius, H. J.; Pieters, R. J. Org. Biomol. Chem. 2003, 1, 803–810.
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5, 971–975.
C21H23N3O7: C, 58.74; H, 5.40; N, 9.79. Found: C, 58.65; H, 5.49;
25. Kolb, H. C.; Sharpless, K. B. Drug Discovery Today 2003, 8, 1128–1137.
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N, 9.71.
4.26. 1-(5-Deoxy-1,2-O-isopropyliden-a-D-xylofuranos-5-yl)-4-
(2H-chromen-2-one-oxymethyl)-1,2,3-1H-triazole (40)
Light brown solid: mp 145–148 °C; yield (1.54 g, 80%); Rf 0.6
(49:1 CHCl3–MeOH); [
a]
ꢀ20 (c 0.1, MeOH); IR (KBr) cmꢀ1
:
D
3400, 2985, 2365, 1685, 1622, 1379, 766; 1H NMR (300 MHz,
CDCl3 + DMSO-d6): d 1.26, 1.39 (s, 6H, CMe2), 3.43 (br s, 1H, OH),
4.14 (d, J 2.6 Hz, 1H, H-3), 4.46 (m, 1H, H-4), 4.49 (d, J 3.6 Hz, 1H,
H-2), 4.58–4.67 (m, 2H, H-5), 5.37 (s, 2H, –OCH2), 5.89 (d, J
3.6 Hz, 1H, H-1), 6.04 (s, 1H, coumarinyl-H-3), 7.27 (dd, J 8.3 Hz,
0.6 Hz, 2H, –ArH), 7.56–7.52 (m, 1H, –ArH), 7.76 (dd, J 8.3 Hz,
0.6 Hz, 1H, –ArH), 8.20 (s, 1H, triazolyl-H); 13C NMR (50 MHz,
CDCl3 + DMSO-d6): d 26.48, 27.09, 49.57, 63.25, 74.08, 79.53,
85.49, 91.78, 104.99, 111.29; 115.54, 116.91, 123.35, 124.68,
126.26, 133.27, 141.41, 153.23, 162.02, 164.85, ESIMS: m/z: 416
(M+H)+; Anal. Calcd for C20H21N3O7: C, 57.83; H, 5.10; N, 10.12.
Found: C, 57.78; H, 5.18; N, 10.08.
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N.A., N.J. and S.K.P. thank CSIR New Delhi for the award of SRF
and RAships. Financial assistance from DRDO New Delhi is grate-
fully acknowledged. We sincerely Thank SAIF division, CDRI for
providing the spectral data and microanalyses. This is CDRI
communication no. 7974.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carres.2010.10.017.
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