Efficient microwave assisted synthesis of novel 1,2,3-triazole-sucrose derivatives by cycloaddition reaction of sucrose azides and terminal alkynes

Article abstract of DOI:10.1016/j.carres.2013.06.017

Novel 1-(1′,2,3,3′,4,4′,6-hepta-O-acetyl-6′-deoxy- sucros-60-yl)-4-substituted-1,2,3-triazoles were synthesized by microwave assisted copper catalyzed 1,3-dipolar cycloaddition of sucrose derived azides with terminal alkynes in excellent yields and in sho

Full text of DOI:10.1016/j.carres.2013.06.017

Carbohydrate Research 379 (2013) 60–67
Contents lists available at SciVerse ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Efficient microwave assisted synthesis of novel 1,2,3-triazole–sucrose
derivatives by cycloaddition reaction of sucrose azides and terminal
alkynes
⇑
Taterao M. Potewar, Krasimira T. Petrova, M. Teresa Barros
REQUIMTE, CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
a r t i c l e i n f o
a b s t r a c t
Novel 1-(10,2,3,30,4,40,6-hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-substituted-1,2,3-triazoles were synthe-
sized by microwave assisted copper catalyzed 1,3-dipolar cycloaddition of sucrose derived azides with
terminal alkynes in excellent yields and in short reaction times. The compound 10,2,3,30,4,40,6-hepta-O-
acetyl-60-azido-60-deoxy-sucrose was regioselectively synthesized from sucrose by improved procedure
and used for the cycloadditions. By combining carbohydrate and 1,2,3-triazole structural motifs, a library
of 1,2,3-triazole–sucrose conjugates have been obtained.
Article history:
Received 23 May 2013
Received in revised form 19 June 2013
Accepted 20 June 2013
Available online 28 June 2013
Keywords:
1,2,3-Triazoles
Ó 2013 Elsevier Ltd. All rights reserved.
Sucrose derived azides
Carbohydrate
Microwave assisted synthesis
‘Click’ chemistry
1,3-Dipolar cycloaddition
1. Introduction
amino sugars, nucleosides, and many other glycosylated heterocy-
cles.23–25 The term ‘click chemistry’ coined by Sharpless and co-
Glycosyl azides are important class of carbohydrate derivatives,
which have been used as precursors for the synthesis of glycosyl
amines,1,2 N-glycopeptides,3 N-glycoproteins,4 and glycosyl het-
erocycles, such as 1,2,3-triazoles.5–7. In some cases, glycosyl azides
have been converted into glycosyl fluorides for their use in the syn-
thesis of oligosaccharides and glycoconjugates.8 Glycosyl azides
have successfully been used in the solid phase preparation of gly-
copeptides.9,10 They can also provide chiral templates for the syn-
thesis of glycosyl amino acids.11–13 Glycosyl azides have been
applied as novel substrate for enzymatic transglycosylations.14
1,2,3-Triazoles and their derivatives have gained significant
amount of attention due to their wide usage in various fields, such
as pharmaceutical, agricultural, material science and biology. The
combination of both carbohydrate and 1,2,3-triazole structural
motifs has led to the flourishing field of conjugates that have
proved to possess various biological activities15–17 Thus, sugar–tri-
azole conjugates were synthesized and tested for glycosidases,18
transsialidase,19 glycogen phosphorylase20 inhibiting activities,
antitubercular activity,21 and as nucleoside mimetics.22
workers,26–28 has opened a new chapter in the area of glycoconju-
gates and macromolecules bearing the triazolyl moiety by cycload-
dition of acetylenic compounds with azides. Copper-catalyzed
triazole synthesis was first reported by Tornoe et al.,29 and this
work is getting great applicability nowadays for selective triazole
synthesis.
Microwave-enhanced synthesis has been extended to almost all
areas of chemistry30 with the exception of carbohydrate chemistry,
which has suffered a certain delay, as it is testified by the limited
number of applications.31,32 In particular, it had previously not
been applied to sucrose chemistry, and the general opinion is that
the method is hampered by competitive degradation of sucrose be-
cause of its thermal instability.33 Herein, a method to overcome
these limitations and to apply highly efficient and fast synthetic
protocols for the synthesis of a series of sugar derivatives under
microwave irradiation is presented.
The key point to successful synthesis under microwave irradia-
tion is to use proper equipment, especially designed for chemical
laboratories. Monomodal microwave equipment has overcome
the uncertainties associated with domestic microwave ovens, as
it offers much more precise control over conditions of temperature
and pressure than any previous technology and the software
provides simplified process monitoring and control, which
results in accurate and reproducible reaction conditions.34 In the
development of new carbohydrates or in their transformations
The azido sugars are known as versatile starting materials in
accessing a number of biologically active compounds, including
⇑
Corresponding author. Tel.: +351 212948300; fax: +351 2948550.
E-mail address: mtb@fct.unl.pt (M.T. Barros).
0008-6215/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carres.2013.06.017

T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
61
there is a need for faster and cleaner methods which can be pro-
vided by microwave heating. The microwave assisted protocols
presented here, allowed significant reduction of time and energy
and potential automatization of tedious multi-step synthesis.
The synthesis of 1,2,3-triazole derived from azido monosaccha-
ride has been extensively investigated, but there are only few re-
ports of 1,2,3-triazoles derived from azido disaccharide.35 To the
best of our knowledge, there is no report on the synthesis of
1,2,3-triazole–sucrose derivatives from 60-azidosucrose derivatives
and alkynes. 10,2,3,30,4,40,6-Hepta-O-acetyl-60-azido-60-deoxy-su-
crose 4 was the key intermediate for the synthesis of 1,2,3-tria-
zole–sucrose derivatives and was prepared regioselectively from
sucrose in four steps, as shown in Scheme 1.
tween 4 and phenyl acetylene 5a in the presence of CuSO4ꢀ5H2O
(0.2 equiv) and sodium ascorbate (0.4 equiv) in tert-BuOH/H2O
(1:1). These conditions have been chosen based on previous exper-
iments. The reaction was carried out at 35, 50, 60, and 70 °C with
conventional heating in an oil bath and under microwave irradia-
tion. The best result was obtained at 70 °C, to afford the corre-
sponding product 6a in 3 h at conventional heating against 5 min
under microwave irradiation of 400 W starting power and atmo-
spheric pressure (Scheme 2), in excellent yield (91.0%) under both
conditions. Further increase of the temperature beyond 70 °C did
not give better results.
The reactions under microwave irradiation were performed
using a monomodal microwave reactor MicroSynth Labstation
(MileStone, USA)34 in open flasks equipped with temperature con-
trol sensor and magnetic stirring. The energy transfer in a micro-
wave-assisted reaction is very quick, that is why only by
programing temperature control the decomposition of the sub-
strates has been avoided and comparatively high yields have been
obtained in short reaction times. In this method, as the tempera-
ture reaches the input value, the power is reduced so that the reac-
tion mixture does not exceed the set point. It then stays at a lower
level in order to maintain the set temperature throughout the en-
tire reaction. Therefore, the reaction conditions are not expressed
as a function of the magnetron power, as for most microwave-as-
sisted reactions published, but by the reaction temperature.
By using these optimized reaction conditions, various alkynes
2. Results and discussion
Initially, 60-O-tert-butyldiphenylsilyl-sucrose 1 was prepared by
treating sucrose with tert-butyldiphenylchlorosilane (TBDPSCl) in
pyridine at room temperature, as previously described.36 Then,
all remaining hydroxyl groups of 1 were protected by treating it
with acetic anhydride in pyridine at room temperature to afford
60-O-tert-butyldiphenylsilyl-10,2,3,30,4,40,6-hepta-O-acetylsucrose
2 in excellent yield (90.4%). The product 2 was identical in all as-
pects as described in the literature.37 The acetyl groups were cho-
sen because of the advantage of removing them in basic media
without affecting the glycosidic bond.
5a–5j were reacted with 60-azido sucrose
4 to afford 1-
To deprotect the silyloxy group, 2 was treated with tetra-n-
butylammonium fluoride (TBAF) in THF at room temperature.
The reaction afforded the desired 10,2,3,30,4,40,6-hepta-O-acetylsu-
crose 3 in 41.0% yield, along with formation of other undesired
products resulting from acyl migration and fluorolysis of acetate
groups. In order to obtain alcohol 3 in enhanced yield, other proce-
dures were attempted, such as performing the deprotection reac-
tion using TBAF at lower temperatures or iodine in acetonitrile at
60 °C, but those did not produce 3 with improved yield. When
selective deprotection of the silyloxy group of 2 with HF-pyridine
in THF at room temperature was tried, it afforded 3 in 81.3% yield
as colorless solid. The reaction procedure and work up were easy to
perform and gave very clean reaction without any acetyl migration,
thus improving the procedures found in the literature.38,39
(10,2,3,30,4,40,6-hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-substi-
tuted-1,2,3-triazoles 6a–6j (Fig. 1) in excellent yields and in short
reaction time (Table 1).
The bi-functionalized compound 10,2,3,30,4,40-hexa-O-acetyl-
6,60-diazido-6,60-dideoxysucrose 9 has been synthesized as previ-
ously described37 via 6,60-dibromo-6,60-dideoxysucrose
7 and
6,60-diazido-6,60-dideoxysucrose 8 (Scheme 3).
Then, using a similar microwave assisted protocol for the cyclo-
addition reactions as described above, two 1-(10,2,3,30,4,40-hexa-O-
acetyl-6,60-dideoxy-sucros-6,60-diyl)-bis-4-substituted-1,2,3-tria-
zoles 10a and 10b have been obtained (Scheme 4, Fig. 1).
All the products are novel and have been characterized by IR, 1H
NMR, 13C NMR, COSY, HMQC, HMBC, [
a]D, melting points, and
It was then successfully converted into 10,2,3,30,4,40,6-hepta-O-
acetyl-60-azido-60-deoxy-sucrose 4 via two step procedure, as
shown in Scheme 1. For this, 3 was treated with methanesulfonyl
chloride in CH2Cl2 using Et3N and DMAP at 0 °C to afford
MALDI TOF MS. This type of sugar–triazole conjugates has proved
to possess a large variety of useful biological activities, as shown in
numerous reports in the scientific literature.6,7,15,19–21,40–43 The tri-
azoles 6g and 6h, which possess polymerizable moieties, could be
polymerized and have potential to produce biodegradable
polymers.44,45
In conclusion, a convenient protocol for microwave assisted
synthesis of 1-(10,2,3,30,4,40,6-hepta-O-acetyl-60-deoxy-sucros-60-
yl)-4-substituted-1,2,3-triazoles and 1-(10,2,3,30,4,40-hexa-O-acet-
yl-6,60-dideoxy-sucros-6,60-diyl)-bis-4-substituted-1,2,3-triazoles
10,2,3,30,4,40,6-hepta-O-acetyl-60-O-methanesulfonyl
sucrose.
Without purifying the mesylate, it was treated with sodium azide
in DMF under microwave irradiation at 120 °C (400 W) for 10 min
to afford 4 in 89.1% yield as colorless solid.
To establish the reaction conditions for the synthesis of 1,2,3-
triazole–sucrose derivatives, a model reaction was carried out be-
OAc
OH
OAc
OH
HF-pyr
Ac2O, pyr
O
O
AcO
AcO
HO
HO
OAc
OH
2 h, rt, 81%
O
O
5 h, rt, 90%
OTBDPS
OTBDPS
OAc
OH
O
O
OAc
OH
2
1
OAc
O
OAc
O
OAc
OAc
OAc
i) MsCl, CH2Cl2, Et3N, rt, 2 h
AcO
AcO
AcO
AcO
OAc
ii) NaN3, DMF, MW 120oC (400W),
10 min, 89%
N3
O
O
OH
OAc
O
OAc
O
OAc
OAc
4
3
Scheme 1. Synthesis of 10,2,3,30,4,40,6-hepta-O-acetyl-60-azido-60-deoxy-sucrose 4.

62
T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
OAc
O
CuSO4.5H2O (0.2 eq)
Na-ascorbate (0.4 eq)
OAc
O
OAc
OAc
N
N
N
AcO
AcO
AcO
+
R
OAc
OAc
O
AcO
O
R
N3
tert-BuOH: H2O (1:1)
OAc
OAc
MW 70oC (400 W), 5 min
O
O
OAc
OAc
6a-6j
4
5a-5j
Scheme 2. Synthesis of 1,2,3-triazole–sucrose derivatives.
OAc
O
OAc
OAc
OAc
OAc
OAc
N
N
N
N
N
N
N
N
O
AcO
AcO
AcO
AcO
O
O
OAc
OAc
O
O
OAc
OAc
6b
6a
OAc
O
OAc
O
OAc
OAc
N
N
N
N
AcO
AcO
AcO
AcO
OAc
OAc
O
O
OAc
OAc
Br
O
O
OAc
OAc
6d
6c
OAc
O
OAc
O
OAc
OAc
OAc
N
N
N
N
N
N
AcO
AcO
AcO
AcO
OAc
O
O
OMe
OAc
OAc
O
O
OAc
OAc
6e
6f
OAc
O
OAc
O
OAc
OAc
OAc
N
N
N
N
N
N
AcO
AcO
AcO
AcO
OAc
O
O
OAc
O
O
OAc
O
O
O
O
OAc
OAc
6g
6h
OAc
OAc
OAc
OAc
OAc
OAc
N
N
N
N
N
N
O
O
AcO
AcO
AcO
AcO
O
O
OAc
O
OAc
O
O
O
OAc
OAc
6j
6i
O
O
N
N
N
N
N
OAc
OAc
N
N
O
N
N
OAc
OAc
AcO
AcO
N
O
O
N
N
AcO
AcO
O
OAc
O
O
O
OAc
OAc
O
10b
10a
OAc
Fig. 1. Library of 1,2,3-triazole–sucrose derivatives synthesized under microwave irradiation.
is here reported for the first time. All new compounds have been
characterized by IR, 1H NMR, 13C NMR, COSY, HMQC, HMBC, [
]D,
melting points, and MALDI TOF MS. The reaction conditions re-
ported here can be applied to a large number of alkynes, thus
expanding further the presented library of derivatives. The utiliza-
tion of microwave irradiation as a more efficient mode of heating
leading to shorter reaction periods was evaluated. It has been
shown that microwave irradiation efficiently promoted the reac-
tions and allowed a great reduction in reaction times, at the same
time affording high yields (82–94%). In the case of sucrose func-
tionalization the elimination of solvent was not recommended as
it led to significantly lower yields because of overheating.
a

T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
63
Table 1
Microwave assisted synthesis of 1,2,3-triazole–sucrose derivatives, 70 °C (400 W), 1 atm, 5 min
Entry
Alkyne 5
R- (see Scheme 2)
Product (see Fig. 1)
Yielda (%)
Mp (°C)
1
2
3
4
5
6
7
8
9
Phenyl acetylene 5a
3-Ethynyltoluene 5b
Phenyl
m-Tolyl
6a
6b
6c
6d
6e
6f
6g
6h
6i
91.0
88.6
86.2
85.5
94.6
93.5
90.7
82.3
85.6
85.9
89.3
91.2
60–61
60–61
57–58
64–65
54–55
87–88
58–59
47–48
53–54
53–54
88–89
59–60
1-Ethynyl-4-bromobenzene 5c
1-Ethynyl-2,4,5-trimethylbenzene 5d
1-Ethynyl-4-(n-pentyl)benzene 5e
2-Ethynyl-6-methoxynaphthalene 5f
Propargyl acrylate 5g
Propargyl methacrylate 5h
Propargyl acetate 5i
Cyclohexylacetylene 5j
4-Bromophenyl
2,4,5-Trimethylphenyl
4-(n-Pentyl)phenyl
6-Methoxynaphthalen-2-yl
Acryloxymethyl
Methacryloxymethyl
Acetoxymethyl
Cyclohexyl
10
11
12
6j
10a
10b
Phenyl acetylene 5a
Propargyl acetate 5i
Phenyl
Acetoxymethyl
a
Isolated yields after column chromatography.
Br
O
OH
OH
OH
NaN3, DMF
MW 145 oC (400W),
10 min, 84%
Ph3P, CBr4, pyr
O
HO
HO
OH
MW 90oC (400W),
10 min, 76%
OH
O
HO
O
Br
HO
OH
OH
O
OH
O
OH
OH
7
N3
N3
O
OAc
OH
(CH3CO)2O, pyr
O
AcO
AcO
HO
HO
OAc
O
OH
MW 90 oC (400W),
5 min, 98%
O
N3
N3
OAc
OH
O
O
OAc
OH
9
8
Scheme 3. Synthesis of 10,2,3,30,4,40-hexa-O-acetyl-6,60-diazido-6,60-dideoxysucrose 9.
R
N
N
N3
O
CuSO4.5H2O (0.3 eq)
Na ascorbate (0.6 eq)
N
OAc
OAc
N
O
N
N
AcO
AcO
AcO
AcO
+
R
OAc
OAc
O
O
R
N3
tert-BuOH: H2O (1:1)
MW 70oC (400 W), 5 min
OAc
OAc
O
O
OAc
OAc
10a,b
5a,i
9
Scheme 4. Synthesis of 1-(10,2,3,30,4,40-hexa-O-acetyl-6,60-dideoxy-sucros-6,60-diyl)-bis-4-substituted-1,2,3-triazoles 10a and 10b.
3.2. 60-O-tert-Butyldiphenylsilyl-10,2,3,30,4,40,6-hepta-O-
acetylsucrose (2)
3. Experimental part
3.1. General
To a cooled solution of 60-O-tert-butyldiphenylsilyl-sucrose 1
(prepared as described)36 (2 g, 3.44 mmol) in pyridine (30 mL) at
0 °C was added acetic anhydride (3.25 mL, 34.40 mmol) dropwise
over 5 min. After completion of addition of acetic anhydride, ice-
water bath was removed and reaction was left stirred at room tem-
perature for 5 h. The reaction progress was monitored by TLC. After
completion, pyridine was distilled off under reduced pressure and
the residue was purified by flash column chromatography (eluent
Reagents and solvents were purified by standard procedures.46
NMR spectra were recorded at 400 MHz in CDCl3, with chemical
shift values (d) in ppm downfield from TMS (0 ppm) as internal
standard. Optical rotations were measured at 25 °C on an AA-
1000 polarimeter (0.5 dm cell) at 589 nm. The concentrations (c)
are expressed in g/100 mL. Melting points were determined with
a capillary apparatus with heating plate Electrothermal type, in
open capillary on Buchi melting Point B-540 apparatus. FTIR spec-
tra were recorded on Perkin-Elmer Spectrum BX apparatus. Mass
Spectra were recorded on GC-TOF-MS (Gas Chromatography-Time
Of Flight-Mass Spectrometer) Micromass, model GCT. The reac-
tions under microwave irradiation were performed using a mono-
modal microwave reactor MicroSynth Labstation (MileStone,
USA)34 in open flasks equipped with temperature control sensor
and magnetic stirring.
Et2O:hexane,
1:1)
to
afford
60-O-tert-butyldiphenylsilyl-
10,2,3,30,4,40,6-hepta-O-acetylsucrose 2 in 90.4% (2.72 g) as color-
less solid.
Mp 50–52 °C; lit.37 52–54 °C.
IR (CHCl3): mmax 3014, 2958, 2859, 1751, 1428, 1369, 1224,
1039 cmꢁ1
.
1H NMR (400 MHz, CDCl3): d ppm 1.06 (s, 9H, –C(CH3)3), 1.97 (s,
3H, CH3), 1.98 (s, 3H, CH3), 2.01 (s, 3H, CH3), 2.05 (s, 3H, CH3), 2.09

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T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
(s, 3H, CH3), 2.10 (s, 3H, CH3), 2.14 (s, 3H, CH3), 3.84–3.86 (m, 2H,
evaporated under reduced pressure. The residue was dissolved in
EtOAc (25 mL) and washed with water. The organic layer was dried
over anhydrous Na2SO4 and concentrated under reduced pressure
to afford crude, which was further purified by flash column chro-
matography (eluent EtOAc:hexane, 2:3) to afford 10,2,3,30,4,40,6-
H-60), 3.96 (d, J1 ,1 = 12.0 Hz, 1H, H-10), 4.09–4.22 (m, 5H, 1H of H-
10, 2H of H-6, H-4 & H-50) 4.83 (dd, J1,2 = 3.6 Hz, J2,3 = 10.4 Hz, 1H, H-
2), 5.03 (t, J4,5 = J5,6 = 10.0 Hz, 1H, H-5), 5.37–5.42 (m, 2H, H-30 & H-
0
0
3), 5.52 (t, J3 ,4 = J4 ,5 = 5.6 Hz, 1H, H-40), 5.64 (d, J1,2 = 3.6 Hz, 1H, H-
2), 7.36–7.44 (m, 6H, ArH), 7.64–7.68 (m, 4H, ArH).
13C NMR (100 MHz, CDCl3): d ppm 19.1 (–C(CH3)3), 20.5 (CH3),
20.7 (CH3), 26.7 (–C(CH3)3), 61.5 (C-10), 62.9 (C-6), 63.8 (C-60),
68.0 (C-5), 68.2 (C-4), 69.7 (C-3), 70.1 (C-2), 75.0 (C-40), 76.1 (C-
30), 81.3 (C-50), 89.6 (C-1), 103.6 (C-20), 127.7, 129.8, 132.9, 135.5
(Ar), 169.4, 169.7, 169.9, 170.0, 170.1, 170.5 (CO).
0
0
0
0
hepta-O-acetyl-60-azido-60-deoxy-sucrose
colorless solid.
4 (925 mg, 89.1%) as
Mp 143–145 °C; lit47 136–141 °C.
IR (CHCl3): mmax 2961, 2103 (N3), 1748 (CO), 1433, 1370, 1223,
1039, 772 cmꢁ1
1H NMR (400 MHz, CDCl3): d ppm 2.02 (s, 3H, CH3), 2.05 (s, 3H,
.
MALDI-TOF MS: Calcd for C42H54O18Si ([M+Na]+): 897.2977,
found 897.3809.
CH3), 2.11 (s, 12H, 4 ꢂ CH3), 2.17 (s, 3H, CH3), 3.51 (dd, J5 ,6 = 4.0 -
0
0
Hz, J6 ,6 = 13.0 Hz,1H, H-60), 3.69–3.74 (m, 1H, H-60), 4.12–4.31 (m,
6H, H-5, H-50, H-1 & H-6), 4.90 (dd, J1,2 = 3.6 Hz, J2,3 = 10.4 Hz, 1H,
0
0
3.3. 10,2,3,30,4,40,6-Hepta-O-acetylsucrose (3)
H-2), 5.06 (t, J3,4 = J4,5 = 9.8 Hz, 1H, H-4), 5.31 (t, J3 ,4 = J4 ,5 = 6.1 Hz,
1H, H-40), 5.45–5.50 (m, 2H, H-3 & H-30), 5.64 (d, J1,2 = 3.4 Hz, 1H,
H-1).
0
0
0
0
To a solution of 60-O-tert-butyldiphenylsilyl-10,2,3,30,4,40,6-hep-
ta-O-acetylsucrose 2 (1 g, 1.14 mmol) in dry THF (15 mL) in plastic
vial was added HF-Pyridine (70%, 1.71 mL) dropwise and reaction
mixture was stirred at room temperature for 2 h. After completion
of reaction as indicated by appearance of new polar spot on TLC
and complete disappearance of the starting material, the reaction
mixture was poured to water (50 mL), neutralized using solid
NaHCO3 and extracted with CH2Cl2 (3 ꢂ 25 mL). The combined or-
ganic layers were dried over anhydrous Na2SO4 and concentrated
under reduced pressure to afford crude, which was further purified
by flash column chromatography (eluent EtOAc:hexane, 3:2) to af-
ford the desired 10,2,3,30,4,40,6-hepta-O-acetylsucrose 3 (590 mg,
81.3%) as colorless solid.
13C NMR (100 MHz, CDCl3): d ppm 20.4, 20.5 (CH3), 52.8 (C-60),
61.9 (C-6), 62.7 (C-10), 68.2 (C-4), 68.5 (C-5), 69.4 (C-3), 70.2 (C-2),
75.7 (C-30 & C-40), 80.1 (C-50), 90.3 (C-1), 103.8 (C-20), 169.5, 169.6,
169.9, 170.0, 170.6 (CO).
MALDI-TOF MS: Calcd for C26H35N3O17 ([M+Na]+): 684.1864,
found 684.6854.
3.5. General procedure for microwave assisted synthesis of
1,2,3-triazole–sucrose derivatives
To a well-stirred solution of sugar monoazide 4 (1 eq) and al-
kyne 5a-j (1.5 eq) in tert-BuOH and H2O (1:1, 2.50 mmol/mL), was
added aqueous suspension (0.5 mL H2O) of CuSO4ꢀ5H2O (0.2 equiv)
and sodium ascorbate (0.4 equiv). The mixture was then subjected
to microwave irradiation of max 400 W at constant temperature
70 °C for 5 min. After completion, the resulting mixture was diluted
with H2O (10 mL) and extracted with EtOAC (3 ꢂ 10 mL). The or-
ganic layer was washed with brine, dried over Na2SO4, and concen-
trated under reduced pressure to give crude residue. The crude
residue was purified by flash column chromatography.
Mp 158–160 °C; lit.38 158–160 °C.
IR (CHCl3): mmax 3491 (br), 2962, 2859, 1748, 1370, 1226,
1040 cmꢁ1
.
1H NMR (400 MHz, CDCl3): d ppm 2.02 (s, 3H, CH3), 2.05 (s, 3H,
CH3), 2.11 (s, 9H, 3 ꢂ CH3), 2.12 (s, 3H, CH3), 2.19 (s, 3H, CH3), 2.75
(s, 1H, OH), 3.64–3.70 (m, 1H, H-60), 3.84 (d, J6 ,6 = 12.0 Hz, 1H, H-
60), 4.07–4.10 (m, 2H, H-10 & H-50), 4.16–4.19 (m, 2H, H-10 & H-6),
4.26–4.28 (m, 2H, H-4 & H-6), 4.88 (dd, J1,2 = 2.4 Hz, J2,3 = 10.0 Hz,
1H, H-2), 5.09 (t, J4,5 = J5,6 = 9.6 Hz, 1H, H-5), 5.41–5.47 (m, 3H, H-
3, H-30 & H-40), 5.68 (d, J1,2 = 2.4 Hz, 1H, H-1).
0
0
3.6. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
phenyl-1,2,3-triazole (6a)
13C NMR (100 MHz, CDCl3): d ppm 20.6 (CH3), 61.1 (C-60), 61.4
(C-6), 63.9 (C-10), 67.9 (C-5), 68.7 (C-4), 69.3 (C-3), 70.2 (C-2),
73.6 (C-30), 76.1 (C-40), 81.6 (C-50), 90.0 (C-1), 103.2 (C-20), 169.4,
169.9, 170.5, 170.6 (CO).
Compound 6a (132 mg, 91.0%) has been obtained from 4
(125 mg, 0.19 mmol) and phenyl acetylene 5a (32
by the general procedure.
lL, 0.28 mmol)
MALDI-TOF MS: Calcd for C26H36O18 ([M+Na]+): 659.18, found
659.70.
Colorless solid; mp 60–61 °C.
½
a 2D5
ꢃ
+41.84 (c 0.5, CHCl3).
3.4. 10,2,3,30,4,40,6-Hepta-O-acetyl-60-azido-60-deoxy-sucrose (4)
IR (CHCl3): 3023, 2959, 2855, 1749, 1485, 1465, 1437, 1370,
1224, 1041 cmꢁ1
.
To a solution of 10,2,3,30,4,40,6-hepta-O-acetylsucrose 3 (1 g,
1.57 mmol) in CH2Cl2 (25 mL) was added Et3N (0.24 mL, 1.72 mmol)
followed by catalytic amount of 4-dimethylamino pyridine (DMAP).
The reaction mixture was cooled to 0 °C in ice-water bath. To this
cooled reaction mixture was added methane sulfonyl chloride
(0.13 mL, 1.64 mmol) dropwise and reaction mixture was stirred
for 30 min at 0 °C followed by stirring at rt for 2 h. After completion
of reaction, as indicated by disappearance of the starting material
and appearance of non-polar spot on TCL, reaction was quenched
with satd solution of NH4Cl and extracted with CH2Cl2 (2 ꢂ 20 mL),
driedover anhydrousNa2SO4, andconcentratedunderreducedpres-
sure to give crude 10,2,3,30,4,40,6-hepta-O-acetyl-60-O-methanesul-
fonyl sucrose (1.42 g), which was used without further purification.
The obtained crude 10,2,3,30,4,40,6-hepta-O-acetyl-60-O-metha-
nesulfonylsucrose (1.42 g) was dissolved in DMF (25 mL), followed
by addition of NaN3 (520 mg, 7.85 mmol) and the reaction was
subjected to microwave irradiation of max 400 W at constant tem-
perature 120 °C for 10 min. After completion of reaction, DMF was
1H NMR (CDCl3, 400 MHz): d ppm 2.04 (s, 3H, CH3), 2.06 (s, 3H,
CH3), 2.07 (s, 3H, CH3), 2.08 (s, 3H, CH3), 2.12 (s, 3H, CH3), 2.12 (s,
3H, CH3), 2.18 (s, 3H, CH3), 3.97 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.14–
4.18 (m, 2H, H-10 & H-6), 4.28–4.35 (m, 2H, H-4 & H-6), 4.50–4.55
(m, 1H, H-50), 4.73–4.78 (m, 1H, H-60), 4.86–4.90 (m, 1H, H-60), 4.96
(dd, J1,2 = 3.6 Hz, J2,3 = 10.4 Hz, 1H, H-2), 5.08 (t, J4,5 = J5,6 = 9.8 Hz,
0
0
1H, H-5), 5.45–5.57 (m, 3H, H-3, H-30
&
H-40), 5.67 (d,
J1,2 = 3.6 Hz, 1H, H-1), 7.32–7.36 (t, JAr3,4 = JAr4,3 = 7.3 Hz, 1H,
ArH4), 7.42–7.46 (t, JAr2,3 = JAr3,4 = 7.3 Hz, 2H, ArH3), 7.86 (d,
JAr2,3 = 7.5 Hz, 2H, ArH2), 7.95 (s, 1H, ArH triazole ring).
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.5
(CH3), 20.6 (CH3), 52.7 (C-60), 62.1 (C-6), 62.7 (C-10), 68.3 (C-5), 69.0
(C-4), 69.2, 70.0 (C-2), 74.9, 75.4 (C-3), 79.2 (C-50), 90.0 (C-1), 103.7
(C-20), 121.1 (C triazole), 125.7 (ArC), 128.2 (ArC), 128.8 (ArC), 130.3
(ArC quart), 147.8 (Cquat triazole ring), 169.5 (CO), 169.73 (CO),
169.9 (CO), 170.0 (CO), 170.2 (CO), 170.3 (CO), 170.5 (CO).
MALDI TOF MS calcd C34H42N3O17: [M+H]+ 764.2514; found
764.2439.

T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
65
3.7. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(m-tolyl)-1,2,3-triazole (6b)
Colorless solid; mp 64–65 °C.
+45.6 (c 0.75, CHCl3).
IR (CHCl3): 3014, 2957, 2864, 2097, 1751, 1556, 1496, 1465,
½ ꢃ
a 2D5
Compound 6b has been obtained (310 mg, 88.6%) from 4
1307, 1223, 1041 cmꢁ1
.
(300 mg, 0.45 mmol) and 3-ethynyltoluene 5b (90
by the general procedure.
l
L, 0.68 mmol)
1H NMR (CDCl3, 400 MHz): d ppm 2.03 (s, 3H, CH3), 2.04 (s,
3H, CH3), 2.06 (s, 3H, CH3), 2.08 (s, 3H, CH3), 2.11 (s, 3H, CH3),
2.11 (s, 3H, CH3), 2.18 (s, 3H, CH3), 2.27 (s, 3H, ArCH3), 2.28
Colorless solid; mp 60–61 °C.
a 2D5
ꢃ
+54.8 (c 0.5, CHCl3).
(s, 3H, ArCH3), 2.40 (s, 3H, ArCH3), 3.97 (d, J1 ,1 = 12.1 Hz, 1H,
0
0
½
IR (CHCl3): 3018, 2965, 2864, 1751, 1451, 1433, 1370, 1229,
H-10), 4.13–4.18 (m, 2H, H-10 & H-6), 4.26–4.35 (m, 2H, H-5
1043 cmꢁ1
.
&
H-6), 4.54–4.59 (m, 1H, H-50), 4.73–4.78 (m, 1H, H-60),
1H NMR (CDCl3, 400 MHz): d ppm 2.04 (s, 3H, CH3), 2.06 (s,
3H, CH3), 2.08 (s, 6H, 2 ꢂ CH3), 2.12 (s, 3H, CH3), 2.13 (s, 3H,
4.87–4.95 (m, 2H, H-2 & H-60), 5.07 (t, J3,4 = J4,5 = 9.8 Hz, 1H,
H-4), 5.45–5.58 (m, 3H, H-40, H-3, H-30), 5.64 (d, J1,2 = 3.4 Hz,
1H, H-1), 7.05 (s, 1H, ArH3), 7.60 (s, 1H, ArH6), 7.83 (s, 1H,
triazole H).
0
0
CH3), 2.18 (s, 3H, CH3), 2.42 (s, 3H, ArCH3), 3.96 (d, J1 ,1 = 12.1 -
Hz, 1H, H-10), 4.14–4.19 (m, 2H, H-10 & H-6), 4.28–4.36 (m, 2H,
H-5 & H-6), 4.50–4.54 (m, 1H, H-50), 4.72–4.78 (m, 1H, H-60),
13C NMR (CDCl3, 100 MHz): d ppm 19.1, 19.3, 20.4, 20.5, 20.6,
52.7 (C-60), 62.1 (C-6), 62.7 (C-10), 68.3 (C-4), 69.0 (C-5), 69.2 (C-
3), 70.0 (C-2), 75.2 (C-30), 75.6 (C-40), 79.3 (C-50), 90.1 (C-1),
103.7 (C-20), 123.1 (CH of triazole), 126.9 (ArCquat), 129.9 (ArH),
132.2 (ArH), 132.5 (ArCquat), 134.2 (ArCquat), 136.7 (ArCquat),
147.0 (Cquat triazole), 169.4, 169.7, 169.9, 170.0, 170.1, 170.2,
170.4 (CO).
4.88 (dd, J5 ,6 = 3.3 Hz, J6 ,6 = 14.3 Hz, 1H, H-60), 4.96 (dd,
J1,2 = 3.5 Hz, J2,3 = 10.4 Hz, 1H, H-2), 5.08 (t, J3,4 = J4,5 = 9.8 Hz,
1H, H-4), 5.45–5.57 (m, 3H, H-40, H-3, H-30), 5.67 (d,
J1,2 = 3.5 Hz, 1H, H-1), 7.16 (d, JAr4,5 = 7.5 Hz, 1H, ArH4), 7.32 (t,
JAr4,5 = JAr5,6 = 7.6 Hz, 1H, ArH5), 7.63 (d, JAr5,6 = 7.7 Hz, 1H,
ArH6), 7.72 (s, 1H, ArH2), 7.93 (s, 1H, triazole H).
0
0
0
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.6
(CH3), 21.4 (ArCH3), 52.8 (C-60), 62.1 (C-6), 62.7 (C-10), 68.2 (C-4),
69.0 (C-5), 69.2 (C-3), 70.0 (C-2), 74.9 (C-30), 75.3 (C-40), 79.2 (C-
50), 90.0 (C-1), 103.6 (C-20), 121.1 (CH of triazole), 122.9 (ArH),
126.4 (ArH), 128.7 (ArH), 129.0 (ArH), 130.0 (ArCquat), 138.5 (ArC-
quat), 147.9 (Cquat triazole), 169.4, 169.7, 169.9, 170.0, 170.2,
170.3, 170.4 (CO).
MALDI TOF MS calcd C37H48N3O17: [M+H]+ 806.2984; found
806.2952.
3.10. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(4-pentylphenyl)-1,2,3-triazole (6e)
Compound 6e (355 mg, 94.6%) has been obtained from 4
MALDI TOF MS calcd for C35H44N3O17: [M+H]+ 778.2671; found
778.2543.
(300 mg, 0.45 mmol) and 1-ethynyl-4-pentylbenzene 5e (130
0.68 mmol) by the general procedure.
lL,
Colorless solid; mp 54–55 °C.
3.8. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(4-bromophenyl)-1,2,3-triazole (6c)
½
a 2D5
ꢃ
+54.4 (c 0.5, CHCl3).
IR (CHCl3): 3022, 2929, 2855, 1749, 1496, 1453, 1433, 1370,
1225, 1043 cmꢁ1
.
Compound 6c (167 mg, 86.2%) has been obtained from 4
(150 mg, 0.23 mmol) and 1-ethynyl-4-bromobenzene 5c (62 mg,
0.34 mmol) by the general procedure.
1H NMR (CDCl3, 400 MHz): d ppm 0.89 (t, JCH3–CH2 = 6.9 Hz,
3H, CH3CH2–), 1.32–1.35 (m, 4H, CH3CH2CH2–), 1.60–1.67 (m,
2H, CH3CH 2CH CH2–), 2.04 (s, 3H, CH3), 2.05 (s, 3H, CH3),
2.07 (s, 3H, CH3), 2.08 (s, 3H, CH3), 2.11 (s, 3H, CH3), 2.12
(s, 3H, CH3), 2.18 (s, 3H, CH3), 2.63 (t, JCH2–CH2 = 7.8 Hz, 2H,
Colorless solid; mp 57.58.
½
a 2D5
ꢃ
+70.4 (c 0.5, CHCl3).
0
0
IR (CHCl3): 3023, 2961, 1753, 1550, 1482, 1456, 1432, 1370,
ArCH2CH2–), 3.96 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.13–4.18 (m,
1226, 1225, 1041 cmꢁ1
.
2H, H-10 & H-6), 4.27–4.35 (m, 2H, H-5 & H-6), 4.49–4.54
1H NMR (CDCl3, 400 MHz): d ppm 2.04 (s, 3H, CH3), 2.06 (s, 3H,
(m, 1H, H-50), 4.72–4.77 (m, 1H, H-60), 4.87 (dd, J5 ,6 = 3.7 Hz,
0
0
0
0
CH3), 2.07 (s, 3H, CH3), 2.08 (s, 3H, CH3), 2.12 (s, 3H, CH3), 2.12 (s,
J6 ,6 = 14.2 Hz, 1H, H-60), 4.96 (dd, J1,2 = 3.6 Hz, J2,3 = 10.4 Hz,
1H, H-2), 5.07 (t, J3,4 = J4,5 = 9.8 Hz, 1H, H-4), 5.44–5.57 (m,
3H, H-40, H-3 & H-30), 5.66 (d, J1,2 = 3.4 Hz, 1H, H-1), 7.25 (d,
JAr2,3 = 8.1 Hz, 2H, ArH3), 7.77 (d, JAr2,3 = 8.1 Hz, 2H, ArH2), 7.91
(s, 1H, thrizole H).
3H, CH3), 2.17 (s, 3H, CH3), 3.96 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.11–
0
0
4.17 (m, 2H, H-10, H-6), 4.29–4.35 (m, 2H, H-5, H-6), 4.48–4.53 (m,
1H, H-50), 4.72–4.78 (m, 1H, H-60), 4.88 (dd, J5 ,6 = 3.6 Hz,
0
0
J6 ,6 = 14.1 Hz, 1H, H-60), 4.95 (dd, J1,2 = 3.6 Hz, J2,3 = 10.5 Hz, 1H,
H-2), 5.07 (t, J3,4 = J4,5 = 10.1 Hz, 1H, H-4), 5.43–5.57 (m, 3H, H-40,
H-3, H-30), 5.65 (d, J1,2 = 3.6 Hz, 1H, H-1), 7.57 (d, JAr2,3 = 8.4 Hz,
1H, Ar-H3), 7.75 (d, JAr2,3 = 8.4 Hz, 1H, Ar-H2), 9.96 (s, 1H, triazole
H).
0
0
13C NMR (CDCl3, 100 MHz):
d ppm 14.0 (CH3CH2), 20.4
(COCH3), 20.5 (COCH3), 20.5 (COCH3), 20.6 (COCH3), 22.5 (CH2),
31.0 (CH2), 31.4 (CH2), 35.6 (ArCH2), 52.7 (C-60), 62.1 (C-6),
62.7 (C-10), 68.3 (C-4), 69.0 (C-5), 69.2 (C-3), 70.0 (C-2), 74.9
(C-30), 75.3 (C-40), 79.2 (C-50), 90.0 (C-1), 103.6 (C-20), 120.8
(CH of triazole), 125.7 (ArH), 127.6 (ArCquat), 128.9 (ArH),
143.2 (ArCquat), 147.9 (Cquat triazole), 169.5, 169.7, 169.9,
170.0, 170.2, 170.3, 170.5 (CO).
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.6
(CH3), 52.8 (C-60), 62.0 (C-6), 62.6 (C-10), 68.3 (C-4), 69.0 (C-5),
69.1 (C-3), 70.1 (C-2), 74.8 (C-30), 75.3 (C-40), 79.2 (C-50), 90.0 (C-
1), 103.7 (C-20), 121.3 (CH of triazole), 122.1 (ArCquat), 127.3
(ArH), 129.2 (ArCquat), 132.0 (ArH), 146.8 (Cquat triazole), 169.4,
169.7, 169.9, 170.0, 170.3, 170.5 (CO).
MALDI TOF MS calcd C39H52N3O17: [M+H]+ 834.3297; found
834.3619.
MALDI TOF MS calcd for C34H41BrN3O17: [M+H]+ 842.1619;
found 842.1614.
3.11. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(6-methoxynaphthalen-2-yl)-1,2,3-triazole (6f)
3.9. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
[(2,4,5-trimethyl)phenyl]-1,2,3-triazole (6d)
Compound 6f (355 mg, 93.5%) has been obtained from 4
(300 mg, 0.45 mmol) and 2-ethynyl-6-methoxynaphthalene 5f
(125 mg, 0.68 mmol) by the general procedure.
Compound 6d (310 mg, 85.5%) has been obtained from 4
(300 mg, 0.45 mmol) and 1-ethynyl-2,4,5-trimethylbenzene 5d
(98 mg, 0.68 mmol) by the general procedure.
Colorless solid; mp 87–88 °C.
½
a 2D5
+47.6 (c 0.5, CHCl3).
ꢃ

66
T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
IR (CHCl3): 3022, 2957, 2855, 1749, 1613, 1552, 1506, 1482,
1H, H-10), 4.11–4.17 (m, 2H, H-10 & H-6), 4.24–4.34 (m, 2H, H-6 &
H-5), 4.46–4.51 (m, 1H, H-50), 4.70–4.75 (m, 1H, H-60), 4.85 (dd,
1455, 1435, 1366, 1221, 1043 cmꢁ1
.
1H NMR (CDCl3, 400 MHz): d ppm 2.04 (s, 3H, CH3), 2.06 (s, 3H,
CH3), 2.08 (s, 6H, 2 ꢂ CH3), 2.12 (s, 3H, CH3), 2.13 (s, 3H, CH3), 2.18
J5 ,6 = 4.0 Hz, J6 ,6 = 14.3 Hz, 1H, H-60), 4.94 (dd, J1,2 = 3.6 Hz,
J2,3 = 10.4 Hz, 1H, H-2), 5.06 (t, J3,4 = J4,5 = 9.9 Hz, 1H, H-4), 5.31 (d,
J = 3.0, 2H, triazole-CH2O), 5.40–5.55 (m, 3H, H-40, H-3, H-30), 5.40
(t, JCH2-O = 1.5 Hz, 1H, CH2=), 5.62 (d, J1,2 = 3.6 Hz, 1H, H-1), 6.13
(s, 1H, CH2=), 7.80 (s, 1H, triazole H).
0
0
0
0
(s, 3H, CH3), 3.94 (s, 3H, OCH3), 3.98 (d, J1 ,1 = 12.1 Hz, 1H, H-10),
4.11–4.20 (m, 2H, H-10 & H-6), 4.30–4.38 (m, 2H, H-5 & H-6),
4.52–4.56 (m, 1H, H-50), 4.76–4.82 (m, 1H, H-60), 4.92 (d,
0
0
J6 ,6 = 14.1 Hz, 1H, H-60), 4.98 (dd, J1,2 = 3.5 Hz, J2,3 = 10.5 Hz, 1H,
H-2), 5.09 (t, J3,4 = J4,5 = 9.8 Hz, 1H, H-4), 5.47–5.58 (m, 3H, H-40,
H-3, H-30), 5.69 (d, J1,2 = 3.4 Hz, 1H, H-1), 7.15–7.19 (m, 2H,
ArH5,7), 7.79–7.82 (m, 2H, ArH3,4), 7.92 (d, JAr7,8 = 8.4 Hz, 1H,
ArH), 8.04 (s, 1H, triazole H), 8.32 (s, 1H, ArH1).
13C NMR (CDCl3, 100 MHz): d ppm 18.4 (–C(CH3)@), 20.3 (–
COCH3), 20.4 (–COCH3), 20.5 (–COCH3), 52.6 (C-60), 57.6 (triazole-
CH2O), 61.1 (C-6), 62.5 (C-10), 68.1 (C-4), 68.9 (C-5), 69.1 (C-3),
69.9 (C-2), 74.9 (C-30), 75.4 (C-40), 79.2 (C-50), 90.0 (C-1), 103.6
(C-20), 125.2 (CH of triazole), 126.1 (CH2@C-CH3), 135.8 (–
C(CH3)@, 142.8 (Cquat triazole), 166.9 (CO), 169.4 (CO), 169.6
(CO), 169.8 (CO), 169.9, 170.0 (CO), 170.1 (CO), 170.3 (CO).
MALDI TOF MS calcd for C33H44N3O19: [M+H]+ 786.2569; found
786.2564.
0
0
13CNMR(CDCl3, 100 MHz):dppm 20.4 (CH3), 20.5 (CH3), 20.6 (CH3),
52.9 (C-60), 55.3 (OCH3), 62.2 (C-6), 62.7 (C-10), 68.3 (C-4), 69.0 (C-5),
69.2 (C-3), 70.0 (C-2), 74.9 (C-30), 75.3 (C-40), 79.2 (C-50), 90.0 (C-1),
103.7 (C-20), 105.7 (ArH) 119.3 (ArH), 121.1 (CH of triazole), 124.3
(ArH). 124.5 (ArH), 125.30 (ArCquat), 127.4 (ArH), 128.9 (ArCquat),
129.7 (ArH), 134.4 (ArCquat), 147.9 (Cquat triazole), 158.0 (ArCquat),
169.5, 169.7, 169.9, 170.0, 170.2, 170.3, 170.5 (CO).
3.14. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(acetoxymethyl)-1,2,3-triazole (6i)
MALDI TOF MS calcd for C39H45N3O18Na: [M+Na]+ 866.2596;
found 866.2590.
Compound 6i (195 mg, 85.6%) has been obtained from 4
(200 mg, 0.30 mmol) and propargyl acetate 5i (75
by the general procedure at 50 °C. The propargyl acetate was added
in two portions.
lL, 0.76 mmol)
3.12. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(acryloxymethyl)-1,2,3-triazole (6g)
Colorless solid; mp 53–54 °C.
Compound 6g (315 mg, 90.7%) has been obtained from 4
½
a 2D5
ꢃ
+72.8 (c 0.5, CHCl3).
IR (CHCl3): 3018, 2965, 1745, 1455, 1433, 1368, 1225,
(300 mg, 0.45 mmol) and propargyl acrylate 5g (75
by the general procedure.
lL, 0.68 mmol)
1039 cmꢁ1
.
Colorless solid; mp 58–59 °C.
1HNMR(CDCl3, 400 MHz):dppm 2.04 (s, 3H, CH3), 2.05 (s, 3H, CH3),
2.09 (s, 9H, 3 ꢂ CH3), 2.12 (s, 3H, CH3), 2.13 (s, 3H, CH3), 2.19 (s, 3H,
½
a 2D5
ꢃ
+53.2 (c 0.5, CHCl3).
IR (CHCl3): 3014, 2961, 2851, 2125, 1749, 1409, 1378, 1225,
CH3), 3.96 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.11–4.16 (m, 2H, H-10 & H-6),
0
0
1043 cmꢁ1
.
4.25–4.33 (m, 2H, H-5 & H-6), 4.45–4.49 (m, 1H, H-50), 4.70–4.75 (m,
1H NMR (CDCl3, 400 MHz): d ppm 2.03 (s, 3H, CH3), 2.04 (s, 3H,
CH3), 2.08 (s, 6H, 2 ꢂ CH3), 2.11 (s, 3H, CH3), 2.12 (s, 3H, CH3), 2.19
1H, H-60), 4.84 (dd, J5 ,6 = 3.8 Hz, J6 ,6 = 14.1 Hz, 1H, H-60), 4.94 (dd,
J1,2 = 3.6 Hz, J2,3 = 10.7 Hz, 1H, H-2), 5.06 (t, J3,4 = J4,5 = 9.9 Hz, 1H, H-
4), 5.23 (d, JH–C–H = 3.9, 2H, –CH2O), 5.39–5.55 (m, 3H, H-40, H-3, H-
30), 5.61 (d, J1,2 = 3.6 Hz, 1H, H-1), 7.77 (s, 1H, triazole H).
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.8
(CH3), 52.8 (C-60), 57.3 (–CH2O), 62.1 (C-6), 62.5 (C-10), 68.2 (C-4),
69.0 (C-5), 69.1 (C-3), 70.1 (C-2), 74.9 (C-30), 75.4 (C-40), 79.3 (C-
50), 90.1 (C-1), 103.7 (C-20), 125.2 (CH of triazole), 142.7 (Cquat tri-
azole), 169.4, 169.7, 169.9, 170.0, 170.1, 170.2, 170.5, 170.7 (CO).
MALDI TOF MS calcd for C31H41N3O19Na: [M+Na]+ 782.2232;
found 782.2226.
0
0
0
0
(s, 3H, CH3), 3.95 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.11–4.16 (m, 2H, H-
0
0
10 & H-6), 4.24–4.33 (m, 2H, H-5 & H-6), 4.45–4.50 (m, 1H, H-50),
4.69–4.75 (m, 1H, H-60), 4.85 (dd, J5 ,6 = 3.8 Hz, J6 ,6 = 14.2 Hz, 1H,
H-60), 4.94 (dd, J1,2 = 3.6 Hz, J2,3 = 10.5 Hz, 1H, H-2), 5.06 (t,
J3,4 = J4,5 = 9.8 Hz, 1H, H-4), 5.32 (d, J = 2.3, 2H, triazole-CH2O),
5.40–5.55 (m, 3H, H-40, H-3, H-30), 5.61 (d, J1,2 = 3.4 Hz, 1H, H-1),
5.86 (dd, JCH-CH2 = 1.3 Hz, JH–C–H = 17.40 Hz, 1H, CH2@), 6.11–6.18
(m, 1H, –CH@), 6.44 (dd, JCH-CH2 = 1.32 Hz, JH–C–H = 17.40 Hz, 1H,
CH2=), 7.80 (s, 1H, triazole H).
0
0
0
0
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.6
(CH3), 52.8 (C-60), 57.4 (CH2), 62.2 (C-6), 62.6 (C-10), 68.2 (C-4),
69.0 (C-5), 69.1 (C-3), 70.0 (C-2), 74.9 (C-30), 75.5 (C-40), 79.3 (C-
50), 90.1 (C-1), 103.7 (C-20), 125.3 (CH of triazole), 127.9 (CH2=),
131.5 (–CH@), 142.6 (Cquat triazole), 165.8 (CO), 169.5 (CO),
169.7 (CO), 169.9 (CO), 170.0 (CO), 170.1 (CO), 170.2 (CO), 170.4
(CO).
3.15. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(cyclohexyl)-1,2,3-triazole (6j)
Compound 6j (152 mg, 85.9%) has been obtained from 4
(150 mg, 0.23 mmol) and cyclohexylacetylene 5j (45
0.34 mmol) by the general procedure.
lL,
MALDI TOF MS calcd C32H41N3O19Na: [M+Na]+ 794.2232; found
794.2226.
Colorless solid; mp 53–54 °C.
½
a 2D5
ꢃ
+80.8 (c 0.5, CHCl3).
3.13. 1-(10,2,3,30,4,40,6-Hepta-O-acetyl-60-deoxy-sucros-60-yl)-4-
(methacryloxymethyl)-1,2,3-triazole (6h)
IR (CHCl3): 3022, 2933, 2855, 1749, 1497, 1433, 1372, 1223,
1043 cmꢁ1
.
1H NMR (CDCl3, 400 MHz): d ppm 1.24–1.82 (m, 10H, –CH2),
2.04 (s, 6H, 2 ꢂ CH3), 2.08 (s, 3H, CH3), 2.09 (s, 3H, CH3), 2.10 (s,
3H, CH3), 2.13 (s, 3H, CH3), 2.19 (s, 3H, CH3), 2.74–2.79 (m, 1H,
Compound 6h (291 mg, 82.3%) has been obtained from 4
(300 mg, 0.45 mmol) and propargyl acrylate 5h (84 mg,
0.68 mmol) by the general procedure.
CH, cyclohexaneCH), 3.98 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.11–4.18
(m, 2H, H-10 & H-6), 4.22–4.33 (m, 2H, H-6, H-5), 4.46–4.50 (m,
1H, H-50), 4.63–4.69 (m, 1H, H-60), 4.78 (dd, J5´,6´ = 3.9 Hz,
J6´,6´ = 14.1 Hz, 1H, H-60), 4.95 (dd, J1,2 = 3.6 Hz, J2,3 = 10.6 Hz, 1H, H-
2), 5.06 (t, J3,4 = J4,5 = 9.8 Hz, 1H, H-4), 5.41–5.54 (m, 3H, H-40, H-3
& H-30), 5.62 (d, J1,2 = 3.5 Hz, 1H, H-1), 7.40 (s, 1H, triazole H).
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.6
(CH3), 25.9 (cyclohexaneCH2), 26.0 (cyclohexaneCH2), 32.8 (cyclo-
0
0
Colorless solid; mp 47–48 °C.
½
a 2D5
ꢃ
+79.2 (c 0.5, CHCl3).
IR (CHCl3): 3022, 2961, 1751, 1435, 1316, 1291, 1225,
1041 cmꢁ1
.
1H NMR (CDCl3, 400 MHz): d ppm 1.94 (s, 3H, CH3 methacryl),
2.04 (s, 6H, 2 ꢂ CH3), 2.08 (s, 3H, CH3), 2.09 (s, 3H, CH3), 2.11 (s,
0
0
3H, CH3), 2.12 (s, 3H, CH3), 2.19 (s, 3H, CH3), 3.97 (d, J1 ,1 = 12.1 Hz,

T. M. Potewar et al. / Carbohydrate Research 379 (2013) 60–67
67
hexaneCH2), 32.9 (cyclohexaneCH2), 35.1 (cyclohexaneCH), 52.5
Acknowledgements
(C-60), 62.1 (C-6), 62.6 (C-10), 68.2 (C-4), 68.9 (C-5), 69.1 (C-3),
70.0 (C-2), 75.0 (C-30), 75.3 (C-40), 79.3 (C-50), 89.9 (C-1), 103.6
(C-20), 120.7 (CH of triazole), 153.6 (Cquat triazole), 169.4, 169.6,
169.9, 170.1, 170.4 (CO).
This work has been supported by Fundação para a Ciência e a
Tecnologia through Grant No. PEst-C/EQB/LA0006/2011. T. M.
Potewar is grateful to Fundação para a Ciência e a Tecnologia for
the pos-doctoral Grant No. SFRH/BPD/65173/2009.
MALDI TOF MS calcd for C34H48N3O17: [M+H]+ 770.2984; found
770.2978.
References
3.16. 1-(10,2,3,30,4,40-Hexa-O-acetyl-6,60-dideoxy-sucros-6,60-
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(122 mg, 0.19 mmol) and phenyl acetylene 5a (64
by the general procedure.
lL, 0.57 mmol)
Colorless solid; mp 88–89 °C.
IR (CHCl3): 3136, 3026, 2965, 1751, 1484, 1464, 1436, 1367,
1221, 1041 cmꢁ1
.
1H NMR (CDCl3, 400 MHz): d ppm 1.97 (s, 3H, CH3), 2.02 (s, 3H,
CH3), 2.04 (s, 3H, CH3), 2.09 (s, 3H, CH3), 2.14 (s, 6H, 2 ꢂ CH3), 3.96
(d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.08 (d, J1 ,1 = 12.0 Hz, 1H, H-10), 4.25
(m, 1H, H-50), 4.39–4.51 (m, 2H, 2xH-6), 4.56–4.64 (m, 2H, H-5 &
H-60), 4.67–4.71 (m, 1H, H-60), 4.80 (dd, J1,2 = 3.5 Hz, J2,3 = 10.4 Hz,
0
0
0
0
0
0
1H, H-2), 4.94 (t, J3,4 = J4,5 = 9.8 Hz, 1H, H-4), 5.30 (t, J3 ,4
=
J4 ,5 = 6.7 Hz, 1H, H-40), 5.38 (d, J3 ,4 = 6.9 Hz, 1H, H-30), 5.51 (t,
J2,3 = J3,4 = 9.9 Hz, 1H, H-3), 5.65 (d, J1,2 = 3.5 Hz, 1H, H-1), 7.27–
7.44 (m, 6H, ArH3,4), 7.79 (d, JAr2,3 = 7.5 Hz, 2H, ArH2), 7.87 (d,
JAr2,3 = 7.5 Hz, 2H, ArH2), 7.92 (s, 1H, ArH triazole ring), 7.97 (s,
1H, ArH triazole ring).
0
0
0
0
13C NMR (CDCl3, 100 MHz): d ppm 20.4 (CH3), 20.5 (CH3), 20.6
(CH3), 20.7 (CH3), 50.7 (C-60), 51.7 (C-6), 61.5 (C-10), 68.9 (C-5),
69.2 (C-4), 69.7, 70.2 (C-2), 75.1, 75.6 (C-3), 79.8 (C-50), 90.1 (C-1),
104.5 (C-20), 121.1, 121.6 (C triazole), 125.6, 125.8 (ArC), 128.2,
128.3 (ArC), 128.8, 128.9 (ArC), 130.0, 130.3 (ArC quart), 147.8
(Cquat triazole ring), 169.4 (CO), 169.8 (CO), 170.0 (CO), 170.2 (CO).
MALDI TOF MS calcd C40H44N6O15: [M]+ 849.2898; found
849.4776.
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3.17. 1-(10,2,3,30,4,40-Hexa-O-acetyl-6,60-dideoxy-sucros-6,60-
diyl)-4-(acetoxymethyl)-1,2,3-triazole (10b)
Compound 10b (345 mg, 91.2%) has been obtained from 9
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by the general procedure.
lL, 1.36 mmol)
Colorless solid; mp 59–60 °C.
IR (CHCl3): 3144, 3014, 2970, 1749, 1434, 1373, 1225, 1043 cmꢁ1
.
1H NMR (CDCl3, 400 MHz): d ppm 2.04 (s, 3H, CH3), 2.06 (s, 6H,
2 ꢂ CH3), 2.08 (s, 6H, 2 ꢂ CH3), 2.10 (s, 3H, CH3), 2.14 (s, 3H, CH3),
2.17 (s, 3H, CH3), 3.93 (d, J1 ,1 = 12.1 Hz, 1H, H-10), 4.01 (d,
0
0
J1 ,1 = 12.1 Hz, 1H, H-10), 4.07–4.12 (m, 1H, H-6), 4.18–4.20 (m,
1H, H-50), 4.35–4.42 (m, 2H, H-6,60), 4.46–4.52 (m, 1H, H-50),
4.58–4.63 (m, 2H, H-6,60), 4.73 (dd, J1,2 = 3.5 Hz, J2,3 = 10.0 Hz, 1H,
H-2), 4.87 (t, J3,4 = J4,5 = 9.9 Hz, 1H, H-4), 5.14 (s, 2H, triazole-CH2a-
O), 5.20 (s, 1H, triazole-CH2bO), 5.22 (s, 1H, triazole-CH2bO), 5.27 (t,
0
0
34. www.milestonesrl.com.
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(t, J2,3 = J3,4 = 9.9 Hz, 1H, H-3), 5.57 (d, J1,2 = 3.5 Hz, 1H, H-1), 7.69
(s, 1H, triazole H), 7.80 (s, 1H, triazole H).
0
0
0
0
0
0
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(CH3), 20.6 (CH3), 20.7 (CH3), 20.8 (CH3), 50.6 (C-60), 51.6 (C-6),
57.4, 57.4 (CH2), 60.9 (C-10), 68.6 (C-4), 69.1 (C-5), 69.5 (C-3),
70.2 (C-2), 75.1 (C-30), 75.9 (C-40), 80.1 (C-50), 90.1 (C-1), 104.7
(C-20), 125.2, 125.6 (CH of triazole), 142.7, 142.9 (Cquat triazole),
169.2 (CO), 169.7 (CO), 169.8 (CO), 169.8 (CO), 169.9 (CO), 170.2
(CO), 170.7 (CO), 170.8 (CO).
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MALDI TOF MS calcd C34H44N6O19Na: [M]+ 841.2695; found
841.3643.