Reaction of glycal derivatives with alcohols in the presence of N-bromosuccinimide and diphenyldiselenide: Preparation of 2-deoxy-2- phenylselenyl glycosides

Article abstract of DOI:10.1016/j.carres.2012.08.009

Reaction of glycal derivatives with alcohols or glycosyl acceptors in the presence of N-bromosuccinimide (NBS) and diphenyldiselenide resulted in the formation of alkyl 2-deoxy-2-phenylselenyl glycosides or disaccharide derivatives in excellent yield. The

Full text of DOI:10.1016/j.carres.2012.08.009

Carbohydrate Research 361 (2012) 41–48
Contents lists available at SciVerse ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Reaction of glycal derivatives with alcohols in the presence of
N-bromosuccinimide and diphenyldiselenide: preparation of
2-deoxy-2-phenylselenyl glycosides
⇑
Abhijit Sau, Anup Kumar Misra
Bose Institute, Division of Molecular Medicine, P-1/12, C.I.T. Scheme VII-M, Kolkata 700054, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 June 2012
Received in revised form 10 August 2012
Accepted 14 August 2012
Available online 21 August 2012
Reaction of glycal derivatives with alcohols or glycosyl acceptors in the presence of N-bromosuccinimide
(NBS) and diphenyldiselenide resulted in the formation of alkyl 2-deoxy-2-phenylselenyl glycosides or
disaccharide derivatives in excellent yield. The reactions are reasonably fast and considerable stereo-
selectivity was observed in the preparation of disaccharide derivatives.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Glycoside
Diphenyl diselenide
2-Deoxy-2-phenylselenyl sugar
N-Bromosuccinimide
Glycal
1. Introduction
of the glycal derivative to form an episelenonium ion reaction
intermediate; (b) attack of a nucleophile to the episelenonium
Glycal derivatives are important intermediates in the prepara-
tion of several biologically important molecules.1–3 They can be
transformed to 2-substituted carbohydrate derivatives exploiting
their enol ether functionalities. Because of the significant role of
the 2-deoxy sugars in the medicinally useful molecules, a number
of attempts were made in the past to synthesize them. 2-Deoxy
glycosides can be conveniently synthesized from glycal derivatives
through the formation of 2-halo,4–7 2-sulfo,8–12 and 2-seleno glyco-
sides.13–15 Since 2-seleno group can be removed easily by reductive
as well as oxidative conditions, 2-seleno glycosides can be consid-
ered as most convenient precursors of 2-deoxy glycosides than
others. As a consequence, a number of reports appeared in the past
to synthesize 2-deoxyglycosides from glycal derivatives via the
formation of 2-selenoglycosides.13–17 In this context, it is worth
mentioning that although 2-seleno glycosides can act as precursors
of 2-deoxy glycosides, which are essential components of many
bioactive molecules, selenium compounds showed toxicity in the
human neuronal cell line through the increase of reactive oxygen
species (ROS)/RNS and apoptosis.18 Conventionally, 2-selenoglyco-
sides were prepared in a two step process: (a) generation of
phenylselenyl cation (PhSe+) and its addition to the double bond
ion to furnish 2-seleno glycosides as anti-addition products. In
most of the cases two isomeric anti-addition products were
obtained depending on the stereochemistry of the episelenonium
ion. For the synthesis of 2-selenoglycosides, phenylselenyl halides
have been used as the source of phenylselenyl cation in the pres-
ence of silver salt.13–17 Earlier, diphenyl diselenide has also been
used as the source of phenylselenyl moiety in combination with
azide salts to generate 2-azido selenides or 2-azido selenoglyco-
sides from alkenes and glycal derivatives respectively in the
presence of (diacetoxyiodo)benzene19–21 or by electrochemical
methods.22,23 In our attempt to prepare alkyl 2-deoxy-2-phenyl-
selenyl glycosides, we sought to explore the reaction of glycal
derivatives with alcohols in the presence of a combination of
N-bromosuccinimide (NBS) and diphenyl diselenide. Earlier NBS
has been used in the carbohydrate chemistry to transform glycal
derivatives into a variety of useful intermediates.24–27 It was envis-
aged that NBS could react with diphenyl diselenide in an oxidative
mechanism [by generating bromonium ion (Br+)] to produce phe-
nylselenyl bromide in situ, which could react with glycal derivative
in the presence of an alcohol or sugar acceptor to furnish 2-deoxy-
2-phenylselenyl glycoside. We report herein the reaction of glycal
derivatives with alcohols in the presence of a combination of NBS
and diphenyl diselenide toward the preparation of alkyl 2-deoxy-
2-phenylselenyl glycosides (Scheme 1).
⇑
Corresponding author. Fax: +91 33 2355 3886.
E-mail address: akmisra69@gmail.com (A.K. Misra).
0008-6215/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carres.2012.08.009

42
A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
R2
selenyl glycosides as major and minor products. According to path
PhSeSePh (1.2 equiv.)
NBS (2.0 equiv.)
R2
R1O
R1O
B (Fig. 2), NBS generates bromonium ion (Br+) in the first step,
which adds to the double bond of the glycal derivative to form
glycal 1,2-bromonium ion adduct, which opens up by diphenyl
diselenide to form trans 2-bromo-1-selenophenyl glycoside
in situ. Recyclization of trans 2-bromo-1-phenylselenyl glycoside
in the second step forms episelenonium ion species, which be-
comes trapped by the alcohol by trans addition to furnish an iso-
meric mixture of 2-deoxy-2-phenylselenyl glycosides as major
and minor products.
O
R1O
R1O
O
R3OH (1.5-2.0 equiv.)
CH3CN; room temp.
25-40 min.; 72-80%
OR3
SePh
R1: Ac, Bn, Me
R2: CH2OR1, Me
R3: alkyl
Scheme 1. Reaction of glycal derivatives with alcohol or glycosyl acceptor in the
presence of a combination of diphenyl diselenide and NBS.
2. Results and discussion
3. Conclusion
In a set of initial experiments, tri-O-acetyl-D-glucal (1) was
allowed to react with a varied quantity of diphenyl diselenide
(0.8–1.5 equiv) and methanol (1.2–3.0 equiv) in CH3CN in the pres-
ence of a different quantity of NBS (1.0–2.0 equiv) at room temper-
ature. After a series of experimentation it was observed that
reaction of 1 with 1.2 equiv of diphenyl diselenide and 2.0 equiv of
methanol in the presence of 1.5 equiv of NBS in CH3CN furnished
methyl 2-deoxy-2-phenylselenyl glycoside as a mixture of two iso-
In conclusion, a straightforward reaction condition for the prep-
aration of 2-deoxy-2-selenoglycosides has been developed from
glycal derivatives using a combination of diphenyl diselenide and
NBS. A series of disaccharide derivatives have also been synthe-
sized with high stereoselectivity. The reaction condition has sev-
eral noteworthy features to be considered as a useful alternative
to the other existing methods such as, operational simplicity,
significantly fast, mild, and less hazardous reaction condition
avoiding the use of highly reactive phenylselenyl chloride and high
yield.
mer (b-D-gluco-(7)/a-D-manno-(8) = 1:3) in excellent yield (82%) at
room temperature in 25 min. Among the most commonly used or-
ganic solvents for example CH3CN, CH2Cl2, Et2O, toluene, THF, and
1,2-(CH2)2Cl2 the best results were obtained using CH3CN as the
reaction medium. To establish the generality of the reaction condi-
4. Experimental
tion, a series of D-glucal derivatives (containing acetoxy, benzoxy,
and methoxy functionalities) were allowed to react with a combi-
nation of diphenyl diselenide and NBS in a variety of alcohols at
room temperature. Excellent yield of the products were obtained
4.1. General methods
All reactions were monitored by thin layer chromatography
over silica gel coated TLC plates. The spots on TLC were visualized
by warming ceric sulfate (2% Ce(SO4)2 in 2 N H2SO4) sprayed plates
in hot plate. Silica gel 230–400 mesh was used for column chroma-
tography. 1H and 13C NMR spectra were recorded on Brucker
Avance 200 and 500 MHz spectrometers using CDCl3 as solvent
and TMS as internal reference unless stated otherwise. Chemical
shift value is expressed in d ppm. ESI-MS were recorded on a
Micromass mass spectrometer. Commercially available grades of
organic solvents of adequate purity are used in all reactions.
in all reactions, which is presented in Table 1. D-galactal and L-
rhamnal derivatives also furnished 2-deoxy-2-phenylselenyl and
2,6-dideoxy-2-phenylselenyl-glycosides, respectively in excellent
yield under similar reaction conditions. The reaction condition
has been further extended toward the preparation of disaccharide
derivatives. In order to establish the requirement of NBS in the
reaction medium, a control experiment has been carried out with-
out using NBS and it was observed that the reaction did not take
place even after 24 h at room temperature, which confirmed the
involvement of NBS in the reaction. The reaction of monosaccha-
ride acceptors with glycal derivatives under similar reaction condi-
tion furnished 2-deoxy-2-phenylselenyl disaccharide derivatives
in excellent yield. Although the reaction of primary sugar alcohols
gave satisfactory yield of the products, the reaction did not proceed
with the secondary sugar alcohols and degradation of starting
materials was observed with time, which could be explained by
considering the steric crowding around the episelenonium transi-
tion state which inhibits the approach of a secondary sugar alcohol.
An isomeric mixture of the products was formed in most of the
4.2. Typical experimental condition
To a solution of tri-O-acetyl-D-glucal (1; 545 mg, 2.0 mmol) in
CH3CN (5 mL) were added alcohol (4.0 mmol) or monosaccharide
acceptor (2.5 mmol), diphenyl diselenide (750 mg, 2.40 mmol),
and NBS (550 mg, 3.09 mmol) and the reaction mixture was
allowed to stir at room temperature for appropriate time as men-
tioned in Table 1. The reaction mixture was diluted with water and
extracted with CH2Cl2. The organic layer was successively washed
with satd. NaHCO3, water, dried (Na2SO4), and concentrated under
reduced pressure. The crude product was purified over SiO2 using
hexane–EtOAc as eluant to give pure individual isomer. Spectral
data of the isolated products are presented below.
cases, the disaccharide derivatives and
were obtained mostly as one major or exclusive product (
no/( -talo isomer). Various functional groups used in the protec-
D-galactal derived products
a
-D
-man-
a-D
tion of carbohydrates remained unaffected under the reaction
condition. The structure of the products was confirmed from their
NMR spectral analysis. It is presumed that the reaction proceeds
through the formation of a episelenonium transition state22 which
becomes trapped with alcohols to furnish two isomers of 2-phenyl-
4.2.1. Methyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-b-D-
glucopyranoside (7)
Colorless oil; ½a D25
ꢀ
+66 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
selenyl glycosides (a-D-manno/talo isomer as major and b-D-glu-
d 7.66–7.28 (m, 5H, Ar-H), 5.13 (t, J = 9.0 Hz each, 1H, H-3), 4.97 (t,
J = 9.0 Hz each, 1H, H-6a), 4.13 (d, J = 8.5 Hz, 1H, H-1), 4.08 (dd,
J = 12.5, 2.5 Hz, 1H, H-6b), 3.54–3.51 (m, 1H, H-5), 3.50 (s, 3H,
OCH3), 3.09 (t, J = 9.0 Hz each, 1H, H-2), 2.09, 2.06, 2.03, (3 s, 9H,
3 COCH3); 13C NMR (CDCl3, 125 MHz): d 170.7, 170.4, 170 (3
COCH3), 136.4–128.7 (Ar-C), 103.2 (C-1), 72.7 (C-3), 71.5 (C-5),
69.8 (C-4), 62.1 (C-6), 57.1 (OCH3), 47.1 (C-2), 20.8, 20.7, 20.6 (3
COCH3); ESI-MS: 483.0 [M+Na]+; Anal. Calcd for C19H24O8Se
(460.06): C, 49.68; H, 5.27. Found: C, 49.52; H, 5.50.
co-/galacto– as minor products). The formation of episelenonium
species may be possible in two ways as presented in the plausible
mechanisms in Figure 1 and Figure 2. According to path A (Fig. 1),
diphenyl diselenide reacts with N-bromosuccinimide (NBS) to gen-
erate phenylselenyl bromide which adds to the double bond of gly-
cal derivative to give an isomeric mixture of episelenonium
species. 1,2-Trans opening of the episelenonium transition states
lead to the formation of an isomeric mixture of 2-deoxy-2-phenyl-

A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
43
Table 1
Reaction of glycal derivatives with alcohols in the presence of a combination of diphenyl diselenide and NBS to furnish 2-deoxy-2-phenylselenyl glycosidesa
Sl. No.
Glycal
Alcohol
Product
Time (min)
Yieldb (%)
Ratio
1:3
b-Gluco–/Galacto–
a
-Manno–/Talo–
OAc
OAc
SePh
O
AcO
AcO
O
O
AcO
AcO
AcO
AcO
AcO
OMe
1
MeOH
25
82
SePh
OMe
7
8
1
OAc
SePh
O
AcO
AcO
O
AcO
AcO
AcO
OEt
2
3
4
1
1
1
EtOH
30
40
40
80
82
84
1:4
1:3
1:3
SePh
928
OEt
1028
OAc
SePh
AcO
O
AcO
O
AcO
AcO
OnBu
OiPr
nBuOH
iPrOH
AcO
OnBu
SePh
11
OAc
12
SePh
O
AcO
O
AcO
AcO
AcO
AcO
OiPr
SePh
13
14
O
O
OH
O
AcO
AcO
AcO
SePh
O
AcO
AcO
AcO
O
O
PhSe
O
O
O
O
O
O
O
5
1
45
78
1:17
O
O
O
O
O
O
15
16
OH
O
AcO
AcO
AcO
AcO
AcO
AcO
SePh
O
O
BnO
BnO
O
SePh
O
BnO
OMe
O
BnO
6
1
40
75
1:18
BnO
BnO
O
BnO
BnO
OMe
BnO
OMe
17
OBn
18
SePh
O
OBn
O
BnO
BnO
O
BnO
BnO
BnO
BnO
BnO
OMe
7
8
MeOH
EtOH
25
30
76
74
1:5
2:7
SePh
OMe
2
19
OBn
20
SePh
BnO
O
BnO
O
BnO
BnO
BnO
OEt
O
2
2
SePh
OEt
21
22
O
O
OH
O
BnO
BnO
BnO
SePh
O
BnO
BnO
BnO
O
PhSe
O
O
O
O
O
O
O
9
45
72
1:15
O
O
O
O
O
O
23
24
OMe
O
OMe
O
SePh
O
MeO
MeO
MeO
MeO
MeO
MeO
MeO
OMe
OiPr
10
11
MeOH
iPrOH
25
25
86
85
1:4
2:7
SePh
OMe
3
25
OMe
26
28
SePh
O
MeO
O
MeO
MeO
MeO
MeO
3
OiPr
SePh
27
(continued on next page)

44
A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
Table 1 (continued)
Sl. No.
Glycal
Alcohol
iPrOH
Product
Time (min)
Yieldb (%)
Ratio
1:15
b-Gluco–/Galacto–
a
-Manno–/Talo–
AcO
AcO
AcO OAc
O
OAc
SePh
OAc
AcO
O
OiPr
SePh
O
AcO
AcO
12
25
77
4
OiPr
29
30
AcO OAc
OAc
AcO
AcO
SePh
O
OnBu
SePh
O
AcO
13
14
4
4
nBuOH
25
25
74
75
1:16
1:15
OnBu
31
32
OAc
OAc
AcO
AcO
AcO
SePh
O
O
AcO
O
Cyclo-hexanol
SePh
O
33
34
OAc
SePh
O
OH
O
AcO
AcO
O
O
O
O
O
O
15
4
—
40
72
—
O
O
O
O
35
OH
O
OAc
AcO
AcO
SePh
O
BnO
BnO
BnO
OMe
O
16
4
—
40
70
—
O
BnO
BnO
BnO
OMe
36
BnO
OH
O
OBn
OBn
O
BnO
SePh
O
BnO
BnO
BnO
BnO
BnO
OMe
5
O
17
—
40
72
—
O
BnO
BnO
BnO
OMe
37
O
OMe
SePh
OMe
O
AcO
AcO
O
AcO
AcO
AcO
AcO
AcO
18
19
MeOH
iPrOH
25
25
82
84
2:7
2:9
AcO
AcO
38
SePh
OiPr
6
39
OiPr
SePh
O
O
6
AcO
40
SePh
41
a
All reactions are carried out at room temperature.
Isolated yield.
b
4.2.2. Methyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-
a
-
D
-
483.0 [M+Na]+; Anal. Calcd for C19H24O8Se (460.06): C, 49.68; H,
5.27. Found: C, 49.50; H, 5.47.
mannopyranoside (8)
Colorless oil; ½a D25
ꢀ
+75 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.57–7.25 (m, 5H, Ar-H), 5.43 (t, J = 9.5 Hz each, 1H, H-4), 5.39
(dd, J = 9.5, 4.5 Hz, 1H, H-3), 5.07 (br s, 1H, H-1), 4.21–4.14 (m,
2H, H-6ab), 3.96–3.93 (m, 1H, H-5), 3.90 (dd, J = 4.5, 1.5 Hz, 1H,
H-2), 3.37 (s, 3H, OCH3), 2.13, 2.03, 1.68 (3 s, 9H, 3 COCH3); 13C
NMR (CDCl3, 125 MHz): d 170.8, 170.2, 169.6 (3 COCH3), 134.3–
127.8 (Ar-C), 101.5 (C-1), 70.9 (C-3), 68.7 (C-4), 67.2 (C-5), 62.6
(C-6), 55.2 (OCH3), 47.9 (C-2), 20.8, 20.7, 20.3 (3 COCH3); ESI-MS:
4.2.3. Ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-b-D-
glucopyranoside (9)
Colorless oil; ½a D25
ꢀ
+56 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.57–7.25 (m, 5H, Ar-H), 5.11 (t, J = 9.0 Hz each, 1H, H-3), 4.94 (t,
J = 9.0 Hz each, 1H, H-4), 4.25 (d, J = 9.0 Hz each, 1H, H-1), 4.22 (dd,
J = 12.0, 5.0 Hz, 1H, H-6a), 4.03 (dd, J = 12.0, 2.5 Hz, 1H, H-6b), 3.89–
3.85 (m, 1H, OCH2a), 3.54–3.51 (m, 1H, H-5), 3.50–3.46 (m, 1H,

A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
45
OR
O
OR
O
PhSe
OR
O
RO
RO
NBS
RO
RO
RO
RO
PhSeBr
PhSeSePh
R1OH
Se
Ph
R1OH
R1OH
OR
R1OH
SePh
O
RO
RO
RO
O
RO
RO
OR1
SePh
OR1
Figure 1. Plausible mechanism for the formation of 2-deoxy-2-phenylselenyl glycoside (Path A).
OR
O
Br
OR
O
OR
O
NBS
RO
RO
RO
RO
RO
RO
Br
PhSeSePh
PhSeSePh
OR
Br
O
RO
RO
RO
O
RO
RO
SePh
Br
SePh
OR
O
Ph
Se
SePh
O
OR
RO
RO
RO
R1OH
OR
R1OH
RO
RO
O
RO
RO
O
OR1
SePh
RO
RO
Se
Ph
OR1
Figure 2. Plausible mechanism for the formation of 2-deoxy-2-phenylselenyl glycoside (Path B).
OCH2b), 3.10 (t, J = 9.0 Hz each, 1H, H-2), 2.02, 2.00, 1.98 (3 s, 9H, 3
COCH3), 1.20 (t, J = 7.0 Hz each, 3H, CH2CH3); 13C NMR (CDCl3,
125 MHz): d 170.7, 170.2, 169.6 (3 COCH3), 136.0–128.4 (Ar-C),
102.6 (C-1), 72.7 (C-3), 71.4 (C-5), 69.8 (C-4), 65.8 (OCH2CH3),
62.2 (C-6), 47.7 (C-2), 20.8, 20.7, 20.6 (3 COCH3), 14.9 (CH2CH3);
ESI-MS: 497.0 [M+Na]+; Anal. Calcd for C20H26O8Se (474.07): C,
50.74; H, 5.54. Found: C, 50.55; H, 5.77.
CH2–), 0.92 (t, J = 7.0 Hz each, 3H, –CH3–); 13C NMR (CDCl3,
125 MHz): d 170.7, 170.6, 170.0 (3 COCH3), 135.8–128.2 (Ar-C),
102.7 (C-1), 72.8 (C-3), 71.4 (C-4), 69.9 (C-5), 69.8 (OCH2), 62.1
(C-6), 47.8 (C-2), 29.6 (CH2), 22.7 (CH2), 20.7, 20.6 (2 C), (3 COCH3),
14.1 (CH3); ESI-MS: 525.1 [M+Na]+; Anal. Calcd for C22H30O8Se
(502.11): C, 52.70; H, 6.03. Found: C, 52.52; H, 6.20.
4.2.6. nButyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-
a-D-
4.2.4. Ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-
a
-
D
-
mannopyranoside (12)
mannopyranoside (10)
Colorless oil; ½a D25
ꢀ
+80 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
Colorless oil; ½a D25
ꢀ
+62 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.58–7.24 (m, 5H, Ar-H), 5.44–5.38 (m, 2H, H-3, H-4), 5.14 (br s,
1H, H-1), 4.19 (dd, J = 12.0, 5.0 Hz, 1H, H-6a), 4.13 (dd, J = 12.0,
2.5 Hz, 1H, H-6b), 3.97–3.94 (m, 1H, H-5), 3.90–3.89 (m, 1H, H-2),
3.66–3.62 (m, 1H, OCH2a), 3.46–3.43 (m, 1H, OCH2b), 2.12, 2.04,
1.67 (3 s, 9H, 3 COCH3), 1.60–1.53 (m, 2H, –CH2–), 1.39–1.33 (m,
2H, –CH2–), 0.94 (t, J = 7.0 Hz each, 3H, CH3); 13C NMR (CDCl3,
125 MHz): d 170.6, 170.6, 169.5 (3 COCH3), 143.3–127.7 (Ar-C),
100.4 (C-1), 71.1 (C-3), 68.8 (C-4), 67.9 (C-5), 67.3 (–OCH2–), 62.6
(C-6), 48.0 (C-2), 29.7 (–CH2–), 20.8, 20.7, 20.3 (3 COCH3), 19.4
(–CH2–), 13.8 (–CH3–); ESI-MS: 525.1 [M+Na]+; Anal. Calcd for
d 7.58–7.25 (m, 5H, Ar-H), 5.44–5.43 (m, 2H, H-3, H-4), 5.19 (br s,
1H, H-1), 4.21 (dd, J = 12.0, 5.0 Hz, 1H, H-6a), 4.14 (dd, J = 12.0,
2.5 Hz, 1H, H-6b), 3.99–3.96 (m, 1H, H-5), 3.90 (br s, 1H, H-2),
3.72–3.68 (m, 1H, CH2a), 3.53–3.49 (m, 1H, CH2b), 2.13, 2.04, 1.68
(3 s, 9H, 3 COCH3), 1.25 (t, J = 7.0 Hz each, 3H, CH2CH3); 13C NMR
(CDCl3, 125 MHz): d 170.8, 170.2, 169.7 (3 COCH3), 134.2–127.8
(Ar-C), 100.3 (C-1), 71.0 (C-3), 68.7 (C-4), 67.4 (C-5), 63.7
(OCH2CH3), 62.6 (C-6), 48.2 (C-2), 20.8, 20.7, 20.3 (3 COCH3), 14.9
(CH2CH3); ESI-MS: 497.0 [M+Na]+; Anal. Calcd for C20H26O8Se
(474.07): C, 50.74; H, 5.54. Found: C, 50.53; H, 5.76.
C22H30O8Se (502.11): C, 52.70; H, 6.03. Found: C, 52.50; H, 6.25.
4.2.5. nButyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-b-
D
-
4.2.7. 2-Propyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-b-D-
glucopyranoside (11)
glucopyranoside (13)
Colorless oil; ½a D25
ꢀ
+7 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
Colorless oil; ½a D25
ꢀ
+10 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
7.64–7.27 (m, 5H, Ar-H), 5.11 (t, J = 9.0 Hz each, 1H, H-3), 4.95 (t,
J = 9.5 Hz each, 1H, H-4), 4.27 (d, J = 9.0 Hz, 1H, H-1), 4.25 (dd,
J = 12.0, 4.5 Hz, 1H, H-6a), 4.04 (dd, J = 12.0, 2.5 Hz, 1H, H-6b),
3.87–3.82 (m, 1H, OCH2a), 3.55–3.51 (m, 1H, H-5), 3.46–3.42 (m,
1H, OCH2b), 3.12 (t, J = 9.0 Hz each, 1H, H-2), 2.04, 2.02, 2.00 (3 s,
9H, 3 COCH3), 1.60–1.58 (m, 2H, –CH2–), 1.40–1.33 (m, 2H, –
d 763–7.24 (m, 5H, Ar-H), 5.14, (t, J = 9.0 Hz each, 1H, H-3), 4.96 (t,
J = 9.5 Hz each, 1H, H-4), 4.48 (d, J = 9.5 Hz, 1H, H-1), 4.26 (dd,
J = 12.0, 5.5 Hz, 1H, H-6a), 4.09 (dd, J = 12.0, 2.5 Hz, 1H, H-6b),
3.98–3.93 (m, 1H, CH(CH3)2), 3.62–3.58 (m, 1H, H-5), 3.18
(t, J = 9.0 Hz each, 1H, H-2), 2.05, 2.00, 1.99 (3 s, 9H, 3 COCH3),
1.22 (d, J = 6.5 Hz, 3H, CH3), 1.83 (d, J = 6.0 Hz, 3H, CH3); 13C NMR

46
A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
(CDCl3, 125 MHz): d 170.7, 170.2, 169.7 (3 COCH3), 135.0–127.9
(Ar-C), 101.7 (C-1), 73.0 (C-3), 72.9 (C-5), 71.4 (C-4), 70.0
(CH(CH3)2), 62.4 (C-6), 48.8 (C-2), 23.2 (CH3), 21.8 (CH3), 20.8,
20.7, 20.6 (3 COCH3); ESI-MS: 511.0 [M+Na]+; Anal. Calcd for
127.6 (Ar-C), 103.7 (C-1), 82.9 (C-3), 79.7 (PhCH2), 75.6 (C-5),
74.9 (PhCH2), 74.7 (PhCH2),, 73.5 (C-4), 68.9 (C-6), 56.9 (OCH3),
50.4 (C-2); ESI-MS: 627.1 [M+Na]+; Anal. Calcd for C34H36O5Se
(604.17): C, 67.65; H, 6.01. Found: C, 67.46; H, 6.20.
C21H28O8Se (488.09): C, 51.75; H, 5.79. Found: C, 51.58; H, 6.00.
4.2.12. Methyl 3,4,6-tri-O-benzyl-2-deoxy-2-phenylselenyl-a-D-
4.2.8. 2-Propyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-a-D-
mannopyranoside (20)
Colorless oil; ½a D25
ꢀ
+17 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
mannopyranoside (14)
Colorless oil; ½a D25
ꢀ
+97 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.64–7.16 (m, 20 H, Ar-H), 4.98 (br s, 1H , H-1), 4.88 (d,
J = 10.5 Hz, 1H, PhCH2), 4.69 (d, J = 12.5 Hz, 1H, PhCH2), 4.58–4.48
(m, 4H, PhCH2), 4.19–4.16 (m, 1H, H-5), 3.84 (t, J = 9.0 Hz each,
1H, H-4), 3.81 (br s, 1H, H-2), 3.80–3.70 (m, 3H, H-3, H-6ab), 3.29
(s, 3H, OCH3); 13C NMR (CDCl3, 125 MHz): d 134.8–127.5 (Ar-C),
101.6 (C-1), 78.9 (C-3), 75.7 (PhCH2), 75.0 (C-5), 73.4 (PhCH2),
71.6 (PhCH2), 71.4 (C-4), 69.2 (C-6), 54.8 (OCH3), 49.4 (C-2); ESI-
MS: 627.1 [M+Na]+; Anal. Calcd for C34H36O5Se (604.17): C,
67.65; H, 6.01. Found: C, 67.48; H, 6.22.
d 7.58–7.25 (m, 5H, Ar-H), 5.44–5.43 (m, 2H, H-3, H-4), 5.27 (br s,
1H, H-1), 4.19 (dd, J = 12.0, 5.0 Hz, 1H, H-6a), 4.13 (dd, J = 12.0, 2.5,
Hz, 1H, H-6b), 4.06–4.02 (m, 1H, H-5), 3.91–3.87 (m, 1H, CH(CH3)2),
3.86–3.85 (m, 1H, H-2), 2.11, 2.04, 1.67 (3 s, 9H, 3 COCH3), 1.22 (d,
J = 6.0 Hz, 3H, CH3), 1.15 (d, J = 6.0 Hz, 3H, CH3); 13C NMR (CDCl3,
125 MHz): d 170.8, 170.2, 169.7 (3 COCH3), 134.1–127.7 (Ar-C),
98.7 (C-1), 71.1 (C-3), 70.5 (C-5), 68.8 (CH(CH3)2), 67.5 (C-5), 62.7
(C-6), 48.6 (C-2), 23.1 (CH3), 21.5 (CH3), 20.8, 20.7, 20.3 (3 COCH3);
ESI-MS: 511.0 [M+Na]+; Anal. Calcd for C21H28O8Se (488.09): C,
51.75; H, 5.79. Found: C, 51.54; H, 6.06.
4.2.13. Ethyl 3,4,6-tri-O-benzyl-2-deoxy-2-phenylselenyl-b-D-
glucopyranoside (21)
4.2.9. 3,4,6-Tri-O-acetyl-2-deoxy-2-phenylselenyl-
mannopyranosyl-(1?6)-1,2:3,4-di-O-isopropylidene-
a
-
D
-
Colorless oil; ½a D25
ꢀ
+11 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
a
-D
-
d 7.64–7.13 (m, 20 H, Ar-H), 4.99 (d, J = 10.5 Hz, 1H, PhCH2), 4.83
(d, J = 10.5 Hz, 1H, PhCH2), 4.78 (d, J = 11.0 Hz, 1H, PhCH2), 4.57–
4.48 (m, 3H, PhCH2), 4.30 (d, J = 9.0 Hz, 1H, H-1), 3.89–3.80
(m, 1H, –CH2a–), 3.70 (dd, J = 12.0, 2.0 Hz, 1H, H-6a), 3.67 (dd,
J = 12.0, 5.0 Hz, 1H, H-6b), 3.57 (t, J = 9.0 Hz, each, 1H, H-3), 3.54
(t, J = 9.0 Hz, each, 1H, H-4), 3.50–3.42 (m, 1H, –CH2b–), 3.38–
3.35 (m, 1H, H-5), 3.16 (t, J = 9.0 Hz each, 1H, H-2), 1.13 (t,
galactopyranose (16)
Colorless oil; ½a D25
ꢀ
ꢁ2 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.57–7.24 (m, 5H, Ar-H), 5.49 (d, J = 4.0 Hz, 1H, H-1A), 5.40 (t,
J = 9.5 Hz each, 1H, H-4B), 5.37 (dd, J = 9.5, 3.0 Hz, 1H, H-3B), 5.20
(br s, 1H, H-1B), 4.59 (dd, J = 8.0, 2.5 Hz, 1H, H-4A), 4.30–4.29 (m,
1H, H-2A), 4.24–4.18 (m, 2H, H-3A, H-6aB), 4.14–4.10 (m, 1H, H-
6
bB), 4.08–4.05 (m, 1H, H-5B), 3.96–3.91 (m, 2H, H-2B, H-5A), 3.76
(dd, J = 10.5, 6.5 Hz, 1H, H-6aA), 3.70 (dd, J = 10.5, 6.5 Hz, 1H, H-
bA), 2.12, 2.03, 1.68 (3 s, 9H, 3 COCH3), 1.53, 1.41, 1.33, 1.31, (4
J = 7.0 Hz each, 3H, CH2CH3); 13C NMR (CDCl3, 125 MHz):
d
138.2–127.6 (Ar-C), 103.1 (C-1), 82.9 (C-3), 79.8 (C-5), 75.7
(PhCH2), 74.9 (PhCH2), 74.8 (C-4), 73.5 (PhCH2), 69.0 (CH2CH3),
65.4 (C-6), 50.9 (C-2), 14.9 (CH3CH2); ESI-MS: 641.1 [M+Na]+; Anal.
Calcd for C35H38O5Se (618.18): C, 68.06; H, 6.20. Found: C, 67.85; H,
6.42.
6
s, 12H, 4 CH3); 13C NMR (CDCl3, 125 MHz): d 170.5, 169.9, 169.4
(3 COCH3), 134.3–127.7 (Ar-C), 109.3 (C(CH3)2), 108.6 (C(CH3)2),
100.5 (C-1B), 96.2 (C-1A), 71.0 (C-3B), 70.9 (C-4B), 70.6 (C-2A),
70.5 (C-3A), 68.9 (C-4A), 67.0 (C-5B), 66.9 (C-6A), 66.3 (C-5A), 62.4
(C-6B), 47.9 (C-2B), 26.1, 26.0, 24.9, 24.5 (4 CH3), 20.9, 20.7, 20.3
(3 COCH3); ESI-MS: 711.1 [M+Na]+; Anal. Calcd for C30H40O13Se
(688.16): C, 52.40; H, 5.86. Found: C, 52.18; H, 6.06.
4.2.14. Ethyl 3,4,6-tri-O-benzyl-2-deoxy-2-phenylselenyl-aD-
mannopyranoside (22)
Colorless oil; ½a D25
ꢀ
+44 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.61–7.13 (m, 20 H, Ar-H), 5.09 (br s, 1H, H-1), 4.87 (d, J = 10.5 Hz,
1H, PhCH2), 4.66 (d, J = 12.5 Hz, 1H, PhCH2), 4.56–4.45 (m, 4H,
PhCH2), 4.21–4.18 (m, 1H, H-5), 3.85 (t, J = 9.0 Hz each, 1H, H-4),
3.89–3.79 (m, 2H, H-6ab), 3.75 (dd, J = 9.0, 4.0 Hz, 1H, H-3), 3.69
(br s, 1H, H-2), 3.67–3.63 (m, 1H, –CH2a–), 3.39–3.35 (m, 1H, –
CH2b–), 1.20 (t, J = 7.0 Hz each, 1H, CH2CH3); 13C NMR (CDCl3,
125 MHz): d 138.5–127.5 (Ar-C), 100.3 (C-1), 79.1 (C-3), 75.8
(C-4), 75.1 (PhCH2), 73.4 (PhCH2), 71.7 (C-5), 71.5 (PhCH2), 69.2
(CH2CH3), 63.1 (C-6), 49.8 (C-2), 15.0 (CH3CH2); ESI-MS: 641.1
[M+Na]+; Anal. Calcd for C35H38O5Se (618.18): C, 68.06; H, 6.20.
Found: C, 67.83; H, 6.45.
4.2.10. Methyl (3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-a-D-
mannopyranosyl)-(1?6)-2,3,4-tri-O-benzyl-a-D-
glucopyranoside (18)
Colorless oil; ½a D25
ꢀ
+82 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.55–7.20 (m, 20 H, Ar-H), 5.40–5.35 (m, 2H, H-3B, H-4B), 5.18 (br
s, 1H, H-1B), 4.97–4.58 (m, 6H, 3 PhCH2), 4.53 (d. J = 3.5 Hz, 1H, H-
1A), 4.06–4.01 (m, 2H, H-6abB), 3.98–3.95 (m, 1H, H-5A), 3.92–3.90
(m, 2H, H-2B, H-4A), 3.77–3.72 (m, 2H, H-5B, H-6aA), 3.63 (d,
J = 10.5 Hz, 1H, H-6bA), 3.49–3.42 (m, 2H, H-2A, H-3A), 3.35 (s, 3H,
OCH3), 2.09, 2.01, 1.69 (3 s, 9H, 3 COCH3); 13C NMR (CDCl3,
125 MHz): d 170.1, 170.0, 169.9 (3 COCH3), 145.6–127.4 (Ar-C),
100.5 (C-1B), 97.8 (C-1A), 82.2 (C-5A), 80.1 (C-2A), 77.6 (C-3A),
75.7 (PhCH2), 74.8 (PhCH2), 73.3 (PhCH2), 70.9 (C-3B), 69.7 (C-4A),
68.9 (C-5B), 67.0 (C-4B), 66.3 (C-6A), 62.3 (C-6B), 55.1 (OCH3), 47.7
(C-2B), 20.7, 20.6, 20.3 (3 COCH3); ESI-MS: 915.2 [M+Na]+; Anal.
Calcd for C46H52O13Se (892.25): C, 61.95; H, 5.88. Found: C,
61.74; H, 6.11.
4.2.15. 3,4,6-Tri-O-benzyl-2-deoxy-2-phenylselenyl-a-D-
mannopyranosyl-(1?6)-1,2:3,4-di-O-isopropylidene-aD-
galactopyranose (24)
Colorless oil; ½a D25
ꢀ
+7 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
7.61–7.14 (m, 20 H, Ar-H), 5.48 (d, J = 4.5 Hz, 1H, H-1A), 5.18 (br s,
1H, H-1B), 4.87, 4.68, (2 d, J = 10.5 Hz each, PhCH2), 4.58–4.56 (m,
1H, H-4A), 4.55–4.47 (m, 4H, PhCH2), 4.28–4.26 (m, 1H, H-2A),
4.20–4.16 (m, 1H, H-5B), 4.14 (dd, J = 8.0, 2.0 Hz, 1H, H-3A), 3.92–
3.88 (m, 1H, H-5A), 3.87–3.84 (m, 2H, H-3B, H-4B), 3.82 (dd,
J = 4.5, 1.5 Hz, 1H, H-2B), 3.78–3.61 (m, 4H, H-6abA, H-6abB), 1.52,
1.47, 1.29 (3 s, 12H, 2 C(CH3)2); 13C NMR (CDCl3, 125 MHz): d
138.5–127.4 (Ar-C), 109.3, 108.5, (2 C(CH3)2), 100.5 (C-1B), 96.3
(C-1A), 78.9 (C-5B), 75.5 (C-4A), 74.9 (PhCH2), 73.4 (PhCH2), 72.0
(C-3B), 71.5 (PhCH2), 70.9 (C-4B), 70.7 (C-3A), 70.6 (C-2A), 69.0 (C-
6B), 65.8 (C-6A), 65.7 (C-5A), 49.6 (C-2B), 26.1, 26.0, 24.9, 24.6
4.2.11. Methyl 3,4,6-tri-O-benzyl-2-deoxy-2-phenylselenyl-b-D-
glucopyranoside (19)
Colorless oil; ½a D25
ꢀ
+51 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.67–7.16 (m, 20 H, Ar-H), 5.05 (d, J = 10.5 Hz, 1H, PhCH2), 4.88
(d, J = 10.5 Hz, 1H, PhCH2), 4.80 (d, J = 11.0 Hz, 1H, PhCH2), 4.62–
4.46 (m, 3H, PhCH2), 4.20 (d, J = 9.0 Hz, 1H, H-1), 3.74–3.67
(m, 2H, H-6ab), 3.59 (t, J = 9.0 Hz each, 1H, H-3), 3.57 (t, J = 9.0 Hz
each, 1H, H-4), 3.47 (s, 3H, OCH3), 3.39–3.36 (m, 1H, H-5), 3.15
(t, J = 9.0 Hz each, 1H, H-2); 13C NMR (CDCl3, 125 MHz): d 138.2–

A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
47
(CH3); ESI-MS: 855.2 [M+Na]+; Anal. Calcd for C45H52O10Se
(832.27): C, 64.97; H, 6.30. Found: C, 64.74; H, 6.46.
5), 67.2 (C-3), 66.7 (C-4), 66.5 (C(CH3)2, 62.1 (C-6), 46.7 (C-2),
23.1, 21.5, (2 CH3), 21.0, 20.9, 20.6 (3 COCH3); ESI-MS: 511.1
[M+Na]+; Anal. Calcd for C21H28O8Se (488.09): C, 51.75; H, 5.79.
Found: C, 51.59; H, 6.0.
4.2.16. Methyl 3,4,6-tri-O-methyl-2-deoxy-2-phenylselenyl-b-D-
glucopyranoside (25)
Colorless oil; ½a D25
ꢀ
+30 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
4.2.21. nButyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-
a-D-
d 7.66–7.23 (m, 5H, Ar-H), 4.12 (d, J = 9.0 Hz, 1H, H-1), 3.64 (s, 3H,
OCH3), 3.60–3.54 (m, 2H, H-6ab), 3.53 (s, 3H, OCH3), 3.43 (s, 3H,
OCH3), 3.39 (s, 3H, OCH3), 3.21–3.16 (m, 2H, H-3, H-5), 3.13 (t,
J = 9.0 Hz each, 1H, H-4), 2.97 (t, J = 9.0 Hz each, 1H, H-2); 13C
NMR (CDCl3, 125 MHz): d 135.7–127.8 (Ar-C), 103.7 (C-1), 84.4
(C-3), 81.1 (C-5), 74.5 (C-4), 71.2 (C-6), 60.5 (OCH3), 60.2 (OCH3),
59.3 (OCH3), 56.8 (OCH3), 49.8 (C-2); ESI-MS: 399.0 [M+Na]+; Anal.
Calcd for C16H24O5Se (376.07): C, 51.20; H, 6.45. Found: C, 51.0; H,
6.67.
talopyranoside (32)
Colorless oil; ½a D25
ꢀ
+27 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.53–7.36 (m, 5H, Ar-H), 5.44 (dd, J = 5.0, 3.0 Hz, 1H, H-3), 5.31
(br s, 1H, H-4), 5.15 (br s, 1H, H-1), 4.22–4.20 (m, 1H, H-5), 4.19–
4.10 (m, 2H, H-6ab), 3.63–3.58 (m, 1H, O–CH2–), 3.51–3.50 (m,
1H, H-2), 3.39–3.35 (m, 1H, O–CH2–), 2.22, 2.08, 2.07 (3 s, 9H, 3
COCH3), 1.56–1.49 (m, 2H, –CH2–), 1.34–1.25 (m, 2H, –CH2–),
0.89 (t, J = 7.4 Hz each, 3H, CH3); 13C NMR (CDCl3, 125 MHz): d
170.2, 169.8, 169.7 (3 COCH3), 133.8–127.6 (Ar-C), 101.8 (C-1),
67.8 (C-5), 67.2 (C-3), 66.6 (C-4), 66.4 (–OCH2–), 62.1 (C-6), 46.4
(C-2), 31.4 (CH2), 21.0, 20.9, 20.7 (3 COCH3), 19.3 (CH2), 13.8
(CH3); ESI-MS: 525.1 [M+Na]+; Anal. Calcd for C22H30O8Se
(502.11): C, 52.70; H, 6.03. Found: C, 52.52; H, 6.22.
4.2.17. Methyl 3,4,6-tri-O-methyl-2-deoxy-2-phenylselenyl-a-D-
mannopyranoside (26)
Colorless oil; ½a D25
ꢀ
+4 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
7.62–7.22 (m, 5H, Ar-H), 4.88 (br s, 1H, H-1), 3.77–3.72 (m, 2H, H-
6ab), 3.64–3.53 (m, 3H, H-2, H-3, H-5), 3.53 (s, 3H, OCH3), 3.43 (s,
4.2.22. Cyclohexyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-
3H, OCH3), 3.35 (s, 3H, OCH3), 3.33 (t, J = 9.0 Hz each, 1H, H-4),
3.29 (s, 3H, OCH3); 13C NMR (CDCl3, 125 MHz): d 134.8–127.6
(Ar-C), 101.5 (C-1), 80.4 (C-3), 77.4 (C-4), 71.8 (C-6), 71.3 (C-5),
60.6 (OCH3), 59.3 (OCH3), 56.8 (OCH3), 54.8 (OCH3), 48.7 (C-2);
ESI-MS: 399.0 [M+Na]+; Anal. Calcd for C16H24O5Se (376.07): C,
51.20; H, 6.45. Found: C, 51.02; H, 6.70.
a-D-talopyranoside (34)
Colorless oil; ½a D25
ꢀ
+48 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.52–7.25 (m, 5H, Ar-H), 5.47–5.45 (dd, J = 5.0, 3.0 Hz, 1H, H-3),
5.32 (br s, 1H, H-4), 5.28 (br s, 1H, H-1), 4.32–4.30 (m, 1H, H-5),
4.18–4.08 (m, 2H, H-6ab), 3.52–3.50 (m, 1H, –CH–), 3.49–3.48 (m,
1H, H-2), 2.22, 2.05, 2.04, (3 s, 9H, 3 COCH3), 1.73–1.64 (m, 4H),
1.36–1.18 (m, 6H); 13C NMR (CDCl3, 125 MHz): d 170.1, 169.9,
169.6 (3 COCH3), 133.5–127.5 (Ar-C), 99.9 (C-1), 77.1 (–CH–),
67.2 (C-5), 66.7 (C-3), 66.5 (C-4), 62.2 (C-6), 46.7 (C-2), 33.2,
31.5, 25.5, 24.2, 23.8, 21.0, 20.9, 20.6 (3 COCH3); ESI-MS: 551.1
[M+Na]+; Anal. Calcd for C24H32O8Se (528.12): C, 54.65; H, 6.11.
Found: C, 54.48; H, 6.30.
4.2.18. 2-Propyl 3,4,6-tri-O-methyl-2-deoxy-2-phenylselenyl-b-
D
-glucopyranoside (27)
Colorless oil; ½a D25
ꢀ
+34 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.63–7.20 (m, 5H, Ar-H), 4.42 (d, J = 9.0 Hz, 1H, H-1), 3.94–3.89
(m, 1H, CH(CH3)2), 3.60 (s, 3H, OCH3), 3.59–3.53 (m, 2H, H-6ab),
3.52 (s, 3H, OCH3), 3.39 (s, 3H, OCH3), 3.23–3.20 (m, 1H, H-5),
3.17 (t, J = 9.0 Hz each, 1H, H-3), 3.12 (t, J = 9.0 Hz each, 1H, H-4),
3.04 (t, J = 9.0 Hz, each 1H, H-2), 1.14 (d, J = 6.0 Hz, 3H, CH3), 1.10
(d, J = 6.0 Hz, 3H, CH3); 13C NMR (CDCl3, 125 MHz): d 134.4–
127.1 (Ar-C), 101.9 (C-1), 84.5 (C-3), 81.2 (C-5), 74.5 (C-4), 71.8
(CH(CH3)2), 71.5 (C-6), 60.4 (OCH3), 60.2 (OCH3), 59.3 (OCH3),
51.0 (C-2), 23.4 (CH3), 21.6 (CH3); ESI-MS: 427.1 [M+Na]+; Anal.
Calcd for C18H28O5Se (404.11): C, 53.60; H, 7.00. Found: C, 53.42;
H, 7.20.
4.2.23. 3,4,6-Tri-O-acetyl-2-deoxy-2-phenylselenyl-
talopyranosyl-(1?6)-1,2:3,4-di-O-isopropylidene-
a-
D-
a-
D-
galactopyranose (35)
Colorless oil; ½a D25
ꢀ
+1 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
7.53–7.24 (m, 5H, Ar-H), 5,46 (d, J = 5.0 Hz, 1H, H-1A), 5.43 (dd,
J = 5.0, 3.0 Hz, 1H, H-3B), 5.33 (br s, 1H, H-4B), 5.22 (br s, 1H, H-
1B), 4.54 (dd, J = 7.5, 2.0 Hz, 1H, H-4A), 4.35–4.33 (m, 1H, H-5B),
4.27–4.26 (m, 1H, H-2A), 4.20–4.16 (m, 1H, H-6aB), 4.13–4.09 (m,
2H, H-3A, H-6bB), 3.91–3.86 (m, 1H, H-5A), 3.76–3.61 (m, 2H, H-
4.2.19. 2-Propyl 3,4,6-tri-O-methyl-2-deoxy-2-phenylselenyl-
a
-
6abA), 3.56–3.55 (m, 1H, H-2B), 2.22, 2.08, 2.07 (3 s, 9H, 3 COCH3),
D
-mannopyranoside (28)
1.48, 1.34, 1.30, 1.24 (4 CH3); 13C NMR (CDCl3, 125 MHz): d
170.1, 169.9, 169.7 (3 COCH3), 133.7–127.6 (Ar-C), 109.3, 108.6
(2 C(CH3)2), 101.8 (C-1B), 96.1 (C-1A), 70.9 (C-3A), 70.6 (C-4A),
70.5 (C-2A), 76.1 (C-3B), 66.9 (C-5B), 66.5 (C-4B), 66.4 (C-5A), 66.2
(C-6A), 62.0 (C-6B), 46.2 (C-2B), 26.1, 25.9, 24.9, 24.5, (4 CH3),
21.0, 20.9, 20.7 (3 COCH3); ESI-MS: 551.1 [M+Na]+; Anal. Calcd
for C30H40O13Se (688.16): C, 52.40; H, 5.86. Found: C, 52.22; H,
6.10.
Colorless oil; ½a D25
ꢀ
+28 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.61–7.23 (m, 5H, Ar-H), 5.09 (br s, 1H, H-1), 3.85–3.81 (m, 1H,
CH(CH3)2), 3.80–3.77 (m, 1H, H-5), 3.71–3.67 (m, 2H, H-6ab), 3.60
(dd, J = 9.0 Hz, 3.0 Hz, 1H, H-3), 3.56 (br s, 1H, H-2), 3.53 (s, 3H,
OCH3), 3.42 (s, 3H, OCH3), 3.36 (s, 3H, OCH3), 3.35 (t, J = 9.0 Hz each,
1H, H-4), 1.55 (d, J = 6.0 Hz, 3H, CH3), 1.03 (d, J = 6.0 Hz, 3H, CH3);
13C NMR (CDCl3, 125 MHz): d 134.4–127.4 (Ar-C), 98.1 (C-1), 80.5
(C-3), 77.6 (C-5), 71.8 (C-6), 71.3 (CH(CH3)2), 68.9 (C-4), 60.5
(OCH3), 59.3 (OCH3), 56.9 (OCH3), 49.2 (C-2), 23.2 (CH3), 21.2
(CH3); ESI-MS: 427.1 [M+Na]+; Anal. Calcd for C18H28O5Se
(404.11): C, 53.60; H, 7.00. Found: C, 53.45; H, 7.22.
4.2.24. Methyl (3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-a-D-
talopyranosyl)-(1?6)-2,3,4-tri-O-benzyl-a-D-glucopyranoside
(36)
Colorless oil; ½a D25
ꢀ
+7 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
4.2.20. 2-Propyl 3,4,6-tri-O-acetyl-2-deoxy-2-phenylselenyl-
a
-
D
-
7.57–7.19 (m, 20 H, Ar-H), 5.38 (dd, J = 5.0, 3.0 Hz, 1H, H-3B), 5.28
(br s, 1H, H-4B), 5.22 (br s, 1H, H-1B), 4.95–4.54 (6 d, J = 11.0 Hz
each, 6H, PhCH2), 4.41 (d, J = 3.5 Hz, 1H, H-1A), 4.17–4.15 (m, 1H,
H-5B), 4.12–4.00 (m, 2H, H-6abB), 3.92 (t, J = 9.5 Hz each, 1H, H-
4A), 3.69–3.61 (m, 3H, H-5A, H-6abA), 3.49–3.48 (m, 1H, H-2B),
3.36–3.32 (m, 2H, H-2A, H-3A), 3.30 (s, 3H, OCH3), 2.20, 2.08, 1.97
(3 s, 9H, 3 COCH3); 13C NMR (CDCl3, 125 MHz): d 170.1, 169.9,
169.8, (3 COCH3), 138.6–127.6 (Ar-C), 101.9 (C-1B), 97.7 (C-1A),
82.1 (C-4A), 80.1 (C-3A), 77.6 (C-2A), 75.7 (PhCH2), 74.8 (PhCH2),
talopyranoside (30)
Colorless oil; ½a D25
ꢀ
+33 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.52–7.25 (m, 5H, Ar-H), 5.45 (dd, J = 5.0, 3.0 Hz, 1H, H-3), 5.31
(br s, 1H, H-4), 5.42 (br s, 1H, H-1), 4.30–4.28 (m, 1H, H-5), 4.17–
4.09 (m, 2H, H-6ab), 3.86–3.81 (m, 1H, CH(CH3)2), 3.48–3.47 (m,
1H, H-2), 2.22, 2.08, 2.04 (3 s, 9H, 3 COCH3), 1.19, 1.40 (2 d,
J = 6.0 Hz each, 1H, 2 CH3); 13C NMR (CDCl3, 500 MHz): d 170.2,
169.9, 169.8 (3 COCH3), 133.6–127.6 (Ar-C), 100.1 (C-1), 70.3 (C-

48
A. Sau, A. K. Misra / Carbohydrate Research 361 (2012) 41–48
73.2 (PhCH2), 69.7 (C-5A), 66.9 (C-3B), 66.7 (C-4B), 66.4 (C-5B), 66.0
(C-6A), 62.0 (C-6B), 55.0 (OCH3), 46.2 (C-2B), 21.0, 20.9, 20.6 (3
COCH3); ESI-MS: 915.2 [M+Na]+; Anal. Calcd for C46H52O13Se
(892.25): C, 61.95; H, 5.88. Found: C, 61.76; H, 6.10.
4.2.29. 2-Propyl 3,4-di-O-acetyl-2-deoxy-2-phenylselenyl-a-L-
rhamnopyranoside (41)
Colorless oil; ½a D25
ꢀ
ꢁ78 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.56–7.22 (m, 5H, Ar-H), 5.35 (dd, J = 9.0, 4.5 Hz, 1H, H-3), 5.18 (t,
J = 9.0 Hz each, 1H, H-4), 5.16 (br s, 1H, H-1), 3.92–3.88 (m, 1H, H-
5), 3.87–3.83 (m, 2H, H-2, (CH(CH3)2), 2.03, 1.66 (2 s, 6H, 2 COCH3),
1.20, 1.18, 1.13 (3 d, J = 6.0 Hz each, 9H, 3 CH3); 13C NMR (CDCl3,
125 MHz): d 170.1, 169.7 (2 COCH3), 134.1–127.5 (Ar-C), 98.2 (C-
1), 72.5 (C-3), 71.1 (C-5), 69.7 (C-4), 66.6 (CH(CH3)2), 48.8 (C-2),
23.2 (CH3), 21.4 (CH3), 20.8, 20.3 (2 COCH3), 17.6 (CH3); ESI-MS:
453.0 [M+Na]+; Anal. Calcd for C19H26O6Se (430.08): C, 53.15; H,
6.10. Found: C, 53.0; H, 6.27.
4.2.25. Methyl (3,4,6-tri-O-benzyl-2-deoxy-2-phenylselenyl-a-D-
talopyranosyl)-(1?6)-2,3,4-tri-O-benzyl-a-D-glucopyranoside
(37)
Colorless oil; ½a D25
ꢀ
+10 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.59–7.18 (m, 35H, Ar-H), 5.27 (br s, 1H, H-1B), 5.11–4.47 (10 d,
J = 11.0 Hz each, 10 H, PhCH2), 4.45 (d, J = 3.0 Hz, 1H, H-1A), 4.40,
4.34 (2 d, J = 11.0 each, 2H, PhCH2), 4.11–4.09 (m, 1H, H-3B),
3.96–3.94 (m, 1H, H-5B), 3.93 (t, J = 9.0 Hz, 1H, H-4A), 3.85 (br s,
1H, H-4B), 3.74–3.61 (m, 4H, H-6abA, H-6abB), 3.58–3.55 (m, 2H,
H-2B, H-5A), 3.38 (dd, J = 9.5, 3.0 Hz, 1H, H-2A), 3.35 (t, J = 9.5 Hz
each, 1H, H-3A), 3.21 (s, 3H, OCH3); 13C NMR (CDCl3, 125 MHz): d
138.7–127.2 (Ar-C), 102.2 (C-1B), 97.6 (C-1A), 82.0 (C-4A), 80.1 (C-
2A), 77 8 (C-3A), 75.8 (PhCH2), 74.9 (PhCH2), 74.6 (PhCH2), 74.5
(C-3B), 73.7 (C-4B), 73.4 (PhCH2), 73.2 (PhCH2), 70.1 (C-5B), 69.8
(C-5A), 69.7 (PhCH2), 69.2 (C-6A), 65.7 (C-6B), 54.9 (OCH3), 47.1
(C-2B); ESI-MS: 1059.3 [M+Na]+; Anal. Calcd for C61H64O10Se
(1036.36): C, 70.71; H, 6.23. Found: C, 70.50; H, 6.46.
Acknowledgements
A.S. thanks CSIR, New Delhi for providing a Senior Research Fel-
lowship. This work was funded by the Department of Science and
Technology (DST), New Delhi (SR/S1/OC-83/2010) and Bose Insti-
tute, Kolkata.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.carres.2012.08.
009.
4.2.26. Methyl 3,4-di-O-acetyl-2,6-dideoxy-2-phenylselenyl-b-L-
glucopyranoside (38)
Colorless oil; ½a D25
ꢀ
ꢁ92 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.65–7.24 (m, 5H, Ar-H), 5.07 (t, J = 9.0 Hz each, 1H, H-4), 4.68 (t,
J = 9.0 Hz each, 1H, H-3), 4.08 (d, J = 9.0 Hz, 1H, H-1), 3.48 (s, 3H,
OCH3), 3.40–3.35 (m, 1H, H-5), 3.05 (t, J = 9.0 Hz each, 1H, H-2),
2.02, 2.01 (2 s, 6H, 2 COCH3), 1.21 (d, J = 6.0 Hz, 3H, CCH3); 13C
NMR (CDCl3, 125 MHz): d 170.4, 169.9 (2 COCH3), 136.3–128.4
(Ar-C), 102.8 (C-1), 74.9 (C-3), 72.8 (C-5), 69.5 (C-4), 56.8 (OCH3),
47.5 (C-2), 20.8, 20.7 (2 COCH3), 17.4 (CCH3); ESI-MS: 425.0
[M+Na]+; Anal. Calcd for C17H22O6Se (402.05): C, 50.88; H, 5.53.
Found: C, 50.70; H, 5.70.
References
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4.2.27. Methyl 3,4-di-O-acetyl-2-deoxy-2-phenylselenyl-a-L-
rhamnopyranoside (39)
Colorless oil; ½a D25
ꢀ
ꢁ57 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.56–7.24 (m, 5H, Ar-H), 5.31 (dd, J = 9.5, 4.5 Hz, 1H, H-3), 5.18 (t,
J = 9.0 Hz each, 1H, H-4), 4.96 (br s, 1H, H-1), 3.90 (br s, 1H, H-2),
3.85–3.80 (m, 1H, H-5), 3.35 (s, 3H, OCH3), 2.02, 1.67 (2 s, 6H, 2
COCH3), 1.21 (d, J = 6.0 Hz, 3H, CCH3); 13C NMR (CDCl3,
125 MHz): d 170.7, 170.0 (2 COCH3), 134.3–127.6 (Ar-C), 101.3
(C-1), 72.2 (C-3), 71.0 (C-5), 66.5 (C-4), 54.9 (OCH3), 48.1 (C-2),
20.8, 20.3 (2 COCH3), 17.7 (CCH3); ESI-MS: 425.0 [M+Na]+; Anal.
Calcd for C17H22O6Se (402.05): C, 50.88; H, 5.53. Found: C, 50.72;
H, 5.75.
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L
-glucopyranoside (40)
Colorless oil; ½a D25
ꢀ
ꢁ10 (c 1.0, CHCl3); 1H NMR (CDCl3, 500 MHz):
´
´
´
´
22. Predojevic, J.; Vukicevic, M. D.; Wurst, K.; Ongania, K.-H.; Laus, G.; Vukicevic, R.
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d 7.61–7.22 (m, 5H, Ar-H), 5.06 (t, J = 9.0 Hz each, 1H, H-3), 4.69 (t,
J = 9.0 each, 1H, H-4), 4.41 (d, J = 9.0 Hz, 1H, H-1), 3.97–3.92 (m, 1H,
CH(CH3)2), 3.47–3.44 (m, 1H, H-5), 3.15 (t, J = 9.0 Hz each, 1H, H-2),
2.00, 1.97 (2 COCH3), 1.19 (d, J = 6.0 Hz, 3H, CH3), 1.15 (d, J = 6.0 Hz,
3H, CH3), 1.13 (d, J = 6.0 Hz, 3H, CH3); 13C NMR (CDCl3, 125 MHz): d
170.1, 169.7 (2 COCH3), 134.9–127.7 (Ar-C), 101.2 (C-1), 74.9 (C-3),
73.0 (C-5), 72.2 (CH(CH3)2), 69.4 (C-4), 49.2 (C-2), 23.4 (CH3), 21.7
(CH3), 20.7 (2 C, COCH3), 17.5 (CH3); ESI-MS: 453.0 [M+Na]+; Anal.
Calcd for C19H26O6Se (430.08): C, 53.15; H, 6.10. Found: C, 53.0; H,
6.27.
23. Vukicevic, R.; Konstantinovic, S.; Mihailovic, M. L. Tetrahedron 1991, 47, 859–
865.
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Taneja, S. C. J. Carbohydr. Chem. 2011, 30, 61–74.
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J.; Thiem, J.; Rauter, A. P. Eur. J. Org. Chem. 2008, 6134–6143.
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Tetrahedron: Asymmetry 2003, 14, 3183–3188.
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