Convenient syntheses of 1,2-trans selenoglycosides using isoselenuronium salts as glycosylselenenyl transfer reagents

Article abstract of DOI:10.1016/j.carres.2012.07.012

Se-glycosyl-isoselenuronium salts such as three and four which can be prepared in one high-yielding step from acetohalogeno sugars proved to be convenient starting materials for the syntheses of a variety of selenoglycosides. Reaction with (ar)alkyl halid

Full text of DOI:10.1016/j.carres.2012.07.012

Carbohydrate Research 360 (2012) 8–18
Contents lists available at SciVerse ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Convenient syntheses of 1,2-trans selenoglycosides using isoselenuronium
salts as glycosylselenenyl transfer reagents
Ambati Ashok Kumar a,b, Tünde Zita Illyés a, Katalin E. Kövér b, László Szilágyi a,
⇑
a Department of Organic Chemistry, University of Debrecen, H-4010 Debrecen Pf.20., Hungary
b Department of Inorganic and Analytical Chemistry, University of Debrecen, H-4010 Debrecen Pf.20., Hungary
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 10 May 2012
Received in revised form 10 July 2012
Accepted 17 July 2012
Available online 25 July 2012
Se-glycosyl-isoselenuronium salts such as three and four which can be prepared in one high-yielding step
from acetohalogeno sugars proved to be convenient starting materials for the syntheses of a variety of
selenoglycosides. Reaction with (ar)alkyl halides proceeds under mild conditions, in short time, at room
temperature to afford the corresponding selenoglycosides in good yields. Aryl halides react to appreciable
extent only if bearing activating nitro groups on the aromatic ring. Reactions with acylating reagents such
as acetic anhydride and benzoyl chlorides furnished anomeric selenoesters some of which were recently
proposed as starting compounds for alternative selenoglycoside syntheses. Selenodisaccharides with two
different monosaccharide units could also be prepared via reactions of glycosyl-isoselenuronium salts
with monosaccharide derivatives bearing primary or secondary triflate groups.
Keywords:
Selenoglycosides
Selenodisaccharides
Isoselenuronium salts
Glycosyl selenocarboxylates
Odorless reagents
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
under reducing conditions11,12,24–28 in lieu of the selenol. One
drawback of this procedure is, however, that it may not be compat-
Selenosugars, including selenoglycosides, are useful in struc-
tural and biochemical investigations of glycosidase enzymes as
hydrolytically stable inhibitors;1–3 some representatives have also
been found as urine metabolites of rat or human origin.4–8 On the
other hand, selenoglycosides play an important role in synthetic
carbohydrate chemistry for example, for the preparation of 2-
deoxy glycosides and orthoesters,9 functionalized glycals,10,11 C-
glycosides12 and other glycoconjugates,13–16 or in controlled glyco-
sylation of proteins.17
ible with protecting groups. These reactions proceed via inversion
at the anomeric carbon and are mainly useful for the preparation of
aryl 1-seleno-b-D-glycosides.
Alternatively, a reactive 1-Se-sugar derivative, typically a glyco-
syl-1-selenolate is prepared first which can subsequently be con-
verted into Se-glycoside via reaction with alkyl-, aryl- or glycosyl
halogenides. Displacement of the bromine of tetra-O-acetyl-a-D-
glucopyranosyl bromide by potassium selenobenzoate (PhCOSeK)
leads to the formation of 1-selenobenzoyl-2,3,4,6-tetra-O-acetyl-
Their most significant usefulness is definitely related to glyco-
sylation strategies based on selective activation of selenoglyco-
sides over thioglycosides which has become a powerful tool in
oligosaccharide syntheses.18–22 Searching for novel, convenient
procedures for selenoglycoside syntheses is, therefore, clearly
justifiable.
b-
D-glucopyranose which is deacylated, on treatment with sodium
methoxide, to the sodium salt of 1-seleno-b-
D-glucose as reported
first by Kocourek et al.29 It was shown recently that the benzoyl
group can be selectively removed from the former product to yield
the reactive b-selenolate anion which reacts in situ with various
electrophiles to yield b-selenoglycosides.30
Early work on the syntheses of aryl- and alkyl selenoglycosides
has been summarized by Witczak and Czernecki.23 Introduction of
selenium at the anomeric carbon is achieved basically by either of
two ways depending on the source of selenium. In the classic Koe-
nigs–Knorr type of reaction the anomeric selenium is provided by
the aglycone, typically an arylselenol/selenolate, through nucleo-
philic attack to a glycosyl halogenide. To avoid unpleasant smell
and toxicity of the Se reagent symmetric diselenides may be used
Glycosyl-1-selenolates are seldom isolated because of easy and
fast oxidation into symmetric diselenides. The analogous thiols/
thiolates are, on the contrary, much less susceptible to oxidation
and can, therefore be readily isolated and handled. 1-Thio-sugars
are most conveniently prepared from per-O-acetylated-S-glyco-
syl-isothiouronium salts, usually by treatment with K2S2O5.31 1-
Thio-glycopyranoses can easily react with various electrophiles
such as alkyl (or aryl) halides to furnish the corresponding thiogly-
cosides.32,33 Thioglycosides can also be obtained in one-pot reac-
tion without isolation of the acetylated 1-thiosugars,34–36 but this
procedure has some disadvantages, such as solubility problems
⇑
Corresponding author.
E-mail address: lszilagyi@tigris.klte.hu (L. Szilágyi).
0008-6215/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carres.2012.07.012

A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
9
and the presence of water in the reaction mixture, as pointed out
by Ibatullin et al.37 These authors therefore proposed to proceed
under water-free conditions in the one-step procedure by replac-
ing the inorganic salts with triethylamine and using acetonitrile
as solvent.
In view of the success of this approach we have envisioned
that Se-glycosyl-isoselenuronium salts might serve as suitable
glycosylselenenyl transfer reagents in selenoglycoside syntheses
particularly because of the extreme sensitivity of glycosyl-1-selen-
olates toward oxidation.38 Early attempts to obtain alkyl/aryl sele-
noglycosides from isoselenuronium salts in a one-pot procedure
using a strong base (KOH) in aqueous solutions led to low yields38
due to the harsh conditions and side reactions. Here we wish to
disclose our results on selenoglycoside syntheses from isoselen-
uronium salts under conditions similar to those used by Ibatullin
et al.37 for the preparation of thioglycosides.
at room temperature the corresponding acetylated selenoglyco-
sides (6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34) could
be isolated in good to excellent yields (Scheme 1, Table 1). No ano-
merization was observed, 1H NMR indicating exclusively b-ano-
meric configurations for all products. O-Deacetylation could be
smoothly achieved under Zemplén conditions to furnish unpro-
tected glycosides (7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31,
33, 35).
Aromatic selenoglycosides are usually prepared by reacting an
aromatic selenol, such as selenophenol with a glycosyl ester (usu-
ally acetate)39 or, better, a selenol generated in situ by reduction
with borohydride from the corresponding diselenide, with a glycosyl
halide.11,12,24–28,40 Nonactivated aromatic halides usually do not re-
act with glycosyl selenols/selenolates. Halobenzenes or -pyridines
activated by nitro-substituents were shown to react with
tetraacetyl-glycosyl selenolate, generated in situ from the corre-
sponding isoselenuronium salt by treatment with KOH, to afford
selenoglycosides in low to moderate yields.38 We have found that
2,4-dinitro-chlorobenzene and 2-chloro-4-nitropyridine afforded
the corresponding aromatic selenoglycosides in reasonable yields
(Table 2, entries 12 and 13) in reactions with 3 under the mild con-
ditions used in the syntheses with (ar)alkyl halides. Even bromo-
benzene reacted, somewhat surprisingly, to give 36 in lower
yield (Table 2, entry 11). Methyl-, methoxy- or cyano-substituted
bromobenzenes were, however, found unreactive or resulted in
complex reaction mixtures under a variety of conditions. Deacety-
lation of 36, 38 proceeded smoothly under Zemplén conditions
(Table 2).
2. Results and discussion
The reactions of Se-glycosyl-isoselenuronium salts with alkyl- and
aralkyl halides were tested first. When 2,3,4,6-tetra-O-acetyl-
b-
D
-glucopyranosyl isoselenuronium bromide 3 or 2-acetamido-
-glucopyranosyl isoselenuronium
2-deoxy-3,4,6,-tri-O-acetyl-b-
D
chloride 4 was allowed to react with various (ar)alkyl halides in
methanol or acetonitrile in the presence 1.1 equiv triethylamine
Se-Glycosyl selenobenzoates are useful glycosylselenenyl trans-
fer reagents for the syntheses of a variety of selenoglycosides30,41
as mentioned. The selenobenzoate salt used for the introduction
of the selenobenzoyl unit has to be prepared separately from ele-
mental selenium and benzoyl chloride.30 We have found that isose-
lenuronium salts 3 and 4 are suitable starting materials for the
preparation of the 1-selenoacetate and 1-selenobenzoates as they
readily reacted with acetic anhydride as well as with unsubstitut-
ed- and a variety of substituted benzoyl chlorides to yield the
corresponding products 42–48 (Table 3) including the p-toluyl
derivative 45 (Table 3, entry 16) which was originally pro-
posed as a convenient starting compound for selenoglycoside
syntheses.30
Finally, isoselenuronium salts 3 and 4 were tested as selenogly-
cosyl-transfer reagents against monosaccharidic substrates bear-
ing OH-groups at primary (5s) or secondary (5t) positions
activated by a triflate leaving group. The reactions proceeded in
both cases under conditions similar to those used for the simple
(ar)alkyl glycosides and afforded the Se-disaccharides 49–51, bear-
ing two different monosaccharide units attached to the glycosidic
selenium atom, in respectable yields (Table 4).
OR1
O
OR1
O
NH2+X-
NH2
i)
R1O
R1O
R1O
R1O
Se
R2
R2
X
1
2
R1 = Ac, R2 =OAc, X = Br
1 = Ac, R2 =NHAc, X = Cl
3
4
R
1 = Ac, R2 =OAc, X = Br
R1 = Ac, R2 =NHAc, X = Cl
R
ii)
OR1
O
R1O
R1O
Se
R
R2
R1 = Ac, R2 =OAc
R1 = Ac, R2 =NHAc
iii)
R
1 = H, R2 =OH
R1 = H, R2 =NHAc
i) (NH2)2C=Se, acetone, reflux
ii) Et3N, MeCN, reagents, rt.
iii) MeONa/MeOH, 10-60 min., rt.
In summary, we have shown that Se-glycosyl-isoselenuronium
salts which can be prepared in one high-yielding step from aceto-
halogeno sugars and commercially available odorless selenourea
are convenient starting materials for the syntheses of a variety of
selenoglycosides. The isoselenuronium reagents are odorless solid
products, with reasonably long shelf lives (in refrigerator) and can
be more conveniently handled than the majority of the smelly and
extremely noxious selenium reagents. Reaction with (ar)alkyl
halides proceeds under mild conditions, in short time at room
temperature to afford the corresponding selenoglycosides in good
yields. Aryl halides react to appreciable extent only if bearing acti-
vating nitro groups on the aromatic ring. Reactions with acylating
reagents such as acetic anhydride and benzoyl chlorides furnished
selenocarboxylates including the p-toluyl derivative which was
recently proposed30 as a convenient starting compound for seleno-
glycoside syntheses. Selenodisaccharides with two different mono-
saccharide units could also be prepared in respectable yields via
Compounds
Reagents
R
X
Br, I
Cl, Br
Cl
5a-j
5k-m
5n-r
5s-t
Alkyl, aralkyl
Aryl
Acyl
Monosaccharide
OTf
residue
Scheme 1. Syntheses of selenoglycosides and analogues.

10
A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
Table 1
(Ar)alkyl selenoglycosides
Entry
1
Reagents
Products
R1
R2
Compd no.
Yield (%)
Ref.
Ac
H
Ac
H
OAc
OH
NHAc
NHAc
6
7
8
9
90
89
93
91
OR1
O
42
42
CH3I
3
4
R1O
R1O
Se CH3
5a
R2
OR1
O
Ac
H
Ac
H
OAc
OH
NHAc
NHAc
10
11
12
13
90
87
89
76
30,38
CH2CH3I
3
4
R1O
R1O
Se
CH3
2
3
5b
R2
Ac
H
Ac
H
OAc
OH
NHAc
NHAc
14
15
16
17
60
88
91
78
Br
3
4
OR1
O
R1O
R1O
Se
Se
R2
5c
Ac
H
Ac
H
OAc
OH
NHAc
NHAc
18
19
20
21
70
87
90
88
OR1
O
Br
3
4
R1O
R1O
4
5
R2
5d
CF3
Ac
H
OAc
OH
22
23
95
92
Br
OR1
O
R1O
R1O
Se
Se
CF3
3
3
3
R2
5e
Ac
H
OAc
OH
24
25
97
78
OR1
O
Br
Cl
R1O
R1O
R2
6
7
Cl
5f
Ac
H
OAc
OH
26
27
93
94
OR1
O
Br
Se
Se
R1O
R1O
Br
R2
Br
5g
OR1
O
Ac
H
Ac
H
OAc
OH
NHAc
NHAc
28
29
30
31
92
96
95
86
Br
3
4
R1O
R1O
NC
8
R2
CN
5h
3
4
OR1
O
Ac
Ac
OAc
NHAc
32
33
98
86
Br
R1O
R1O
Se
Se
9
O2N
R2
NO2
5i
Ac
H
OAc
OH
34
35
65
86
OR1
O
Br
R1O
R1O
37
MeO
10
3
R2
OMe
5j
nucleophilic displacement reactions of glycosyl-isoselenuronium
salts with monosaccharide derivatives bearing primary or second-
ary triflate groups.
plates were visualized under UV light and by gentle heating. For
column chromatography Kieselgel 60 (Merck, particle size 0.063–
0.200) was used.
3. Experimental
3.2. Synthetic procedures
3.1. General methods
3.2.1. General procedure for 2,3,4,6-tetra-O-acetyl-
glucopyranosyl selenoglycosides
NMR spectra were recorded on a Bruker Avance II (500/
125 MHz for 1H/13C) spectrometer. Chemical shifts are referenced
2,3,4,6-Tetra-O-acetyl-b-
D
-glucopyranosyl
isoselenuronium
-gluco-
77
to internal TMS (1H), or to the residual solvent signals (13C).
bromide (3) was prepared from 2,3,4,6-tetra-O-acetyl-
a
-D
pyranosyl bromide according to a literature procedure.38 To a stir-
red solution of 3 (1 equiv) in MeCN, Et3N (1.1 equiv) and reagents
(1 equiv, Scheme 1) were added at room temperature. The reaction
mixtures were stirred until TLC indicated consumption of the
starting materials. The reaction mixtures were evaporated under
Se-NMR spectra were referenced to Ph2Se2. Mass spectra were
measured using a Bruker microtofq mass spectrometer. Optical
rotations were determined with a Perkin–Elmer 241 polarimeter.
A Vario MICRO CUBE instrument was used for elemental analyses.
TLC was performed on DC-Alurolle Kieselgel F254 (Merck), and the

A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
11
Table 2
Aryl selenoglycosides
Entry
Reagents
Br
Products
R1
R2
Compd no.
Yield (%)
Ref.
19
Ac
H
OAc
OH
36
37
49
83
OR1
O
R1O
R1O
Se
Se
Se
11
3
3
R2
5k
Cl
O2N
Ac
H
OAc
OH
38
39
64
86
38
OR1
O
NO2
R1O
R1O
NO2
12
R2
NO2
5l
3
4
Ac
Ac
OAc
NHAc
40
41
88
87
Cl
N
OR1
O
38
N
R1O
R1O
NO2
R2
13
NO2
5m
Table 3
Glycosyl selenocarboxylates
Entry
Reagents
Products
R1
R2
Compd no.
Yield (%)
Ref.
Ac2O
5n
3
4
O
O
Ac
Ac
OAc
NHAc
42
43
55
89
OR1
O
R1O
R1O
Se
Se
CH3
14
R2
O
OR1
O
Cl
O
R1O
R1O
15
16
3
Ac
OAc
44
60
R2
5o
5p
30
3
4
O
O
Ac
Ac
OAc
NHAc
45
46
74
56
OR1
O
Cl
R1O
R1O
Se
Se
R2
O
OR1
O
Cl
R1O
R1O
R2
NO2
17
18
3
3
Ac
Ac
OAc
OAc
47
48
70
66
NO2
5q
O
O
OR1
O
Cl
R1O
R1O
Se
R2
Cl
Cl
5r
reduced pressure and the residues purified by column chromatog-
raphy (6:4 hexane/EtOAc).
refluxed in acetone (6 mL) under argon atmosphere for 30 min.
After cooling, the crude product was filtered, washed with acetone.
Recrystallization from acetone gave 4 as a white solid, 2 g (69%),
3.2.2. 2-Acetamido-2-deoxy-3,4,6-tri-O-acetyl-b-
D-
mp 108–110 °C;
½
a 2D2
ꢀ
ꢁ29 (c 0.1, CHCl3); 1H NMR (D2O,
glucopyranosylisoselenuronium chloride (4)
500 MHz): d5.51 (d, 1H, H-1, J1,2 10.9 Hz); 5.24 (t, 1H, H-3, J3,4
9.8 Hz); 5.10 (t, 1H, H-4, J4,5 9.7 Hz); 4.33–4.27 (overlapping sig-
nals, 2H, H-2, H-6a); 4.20 (dd, 1H, H-6b, J5,6b 2.3 Hz); 4.08 (m,
2-Acetamido-2-deoxy-3,4,6-tri-O-acetyl-
a-D-glucopyranosyl
chloride (2 g, 5.9 mmol) and selenourea (0.729 g, 5.9 mmol) were

12
A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
Table 4
Se-disaccharides
Entry
Reagents
OTf
Products
R1
R2
Compd no.
Yield (%)
Ref.
30
3
4
Ac
Ac
OAc
NHAc
49
50
62
57
O
OR1
O
O
R1O
R1O
Se
O
O
R2
19
O
O
O
O
O
O
5s
OBn
OR1
O
O
R1O
R1O
S
e
TfO
AcO
OBn
O
OAc
OMe
R2
R1O
20
4
Ac
NHAc
51
71
R1O
OMe
5t
1H, H-5); 2.05, 2.02, 2.00 (s, 3H, 3x OCOCH3), 1.92 (s, 3H,
NHCOCH3); 13C NMR (D2O, 125 MHz): d 174.2, 173.6, 173.3
(COCH3); 81.3 (C-5); 77.3 (C-1); 73.7 (C-4); 68.7 (C-3); 62.1 (C-
6); 53.4 (C-2); 22.4, 20.6 (OCOCH3); 20.5 (NHCOCH3); 77Se NMR
(D2O, 95.4 MHz): d 486. Anal. Calcd for C15H24ClN3O8Se: C, 36.86;
H, 4.95. Found: C, 36.78; H, 4.82. HRMS m/z Calcd for:
5.08 (overlapping signals 2H, H-2, H-4); 4.64 (d, 1H, H-1, J1,2
10.1 Hz); 4.24 (dd, 1H, H-6a, J5,6a 4.8 Hz, J6a,6b 12.3 Hz); 4.14 (dd,
1H, H-6b, J5,6b 2.3 Hz); 3.75 (m, 1H, H-5); 2.00 (s, 3H, SeCH3); 13C
NMR (CD3OD, 125 MHz): d 83.2 (C-5), 81.6 (C-1), 79.5 (C-3), 74.8
(C-4), 71.5 (C-2), 62.9 (C-6), 2.6 (SeCH3); 77Se NMR (CD3OD,
95.4 MHz): d191. HRMS m/z Calcd for: C7H14O5Se [M+Na]+:
280.990. Found: 280.987.
C
15H24N3O8Se [M]+: 454.065. Found: 454.074.
3.2.7. Methyl 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-1-seleno-
3.2.3. General procedure for 2-acetamido-2-deoxy-3,4,6-tri-O-
acetyl-b- -glucopyranosyl selenoglycosides
b-D
-glucopyranoside (8)42
D
From
4 (100 mg, 0.20 mmol), iodomethane (5a, 29 mg,
To a stirred suspension of 4 (1 equiv) in MeCN (1 mL), Et3N
(1.1 equiv) and reagents (1 equiv, Scheme 1) were added at room
temperature. The reaction mixtures were further stirred at room
temperature for 10–60 min. (monitoring by TLC), and then concen-
trated under reduced pressure. The residues were dissolved in
CH2Cl2, washed with water, dried (Na2SO4), filtered, evaporated
under reduced pressure, and purified by column chromatotgraphy
(2:8 hexane/EtOAc).
0.20 mmol) and Et3N (28 lL, 0.21 mmol), 80 mg (93%), white solid,
mp 195–197 °C, lit.42 192–195 °C, ½a D22
ꢀ
ꢁ51 (c 0.1, CHCl3), lit.42ꢁ31
(c 1.2, DMSO); 1H NMR (CDCl3, 500 MHz): d 5.62 (d, 1H, NH); 5.15,
5.08 (overlapping signals H-4, H-3); 4.70 (d, 1H, H-1, J1,2 10.3 Hz);
4.26 (dd, 1H, H-6a, J5,6a 9.2 Hz, J6a,6b 12.3 Hz); 4.20 (t, 1H, H-2); 4.11
(d, 1H, H-6b); 3.70 (m, H-5); 2.45 (s, 3H, SeCH3); 2.09, 2.05, 2.03 (s,
9H, 3 ꢂ OCOCH3); 1.95 (s, 3H, NHCOCH3); 13CNMR (CDCl3, 125 Hz):
d 171.3, 170.6, 169.9, 169.1 (COCH3); 78.7 (C-1); 76.9 (C-5); 73.7
(C-3); 68.2 (C-4); 62.2 (C-6); 53.3 (C-2); 23.2 (NHCOCH3); 20.7,
20.6, 20.5 (OCOCH3); 2.61 (SeCH3); 77Se NMR (CDCl3, 95.4 MHz):
d217. Anal. Calcd for C15H23NO8Se: C, 42.35; H, 5.41; N, 3.29.
Found: C, 42.37; H, 5.89; N, 3.32. HRMS m/z Calcd for: C15H23NO8Se
[M+Na]+: 448.048. Found: 448.050.
3.2.4. General procedure for unprotected seleno-b-D-
glucopyranosides
The per-O-acetylated derivatives (1 equiv, Tables 1 and 2) were
dissolved in MeOH and catalytic amounts of NaOMe added. After
15–60 min. (monitoring by TLC), the reaction mixtures were neu-
tralized with Amberlyst 15 ion-exchange resin, filtered, and evap-
orated under reduced pressure.
3.2.8. Methyl 2-acetamido-2-deoxy-1-seleno-b-D-
glucopyranoside (9)42
From 8 (80 mg, 0.19 mmol), 51 mg (91%), solid, mp 186-188 °C,
lit.42 188-189 °C, ½a 2D2
ꢀ
ꢁ15 (c 0.1, H2O, lit.42ꢁ26 (c 0.8, H2O); 1H
3.2.5. Methyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (6)
NMR (CD3OD, 500 MHz): d4.68 (dd, 1H, H-1, J1,2 10.1 Hz); 3.91
(dd, 1H, H-6b, J5,6b 1.5 Hz); 3.35 (t, 1H, H-2); 3.65 (dd, 1H, H-6a,
J5,6a 5.7 Hz, J6a,6b 11.3 Hz); 3.45 (t, 1H, H-3, J2,3 9.2 Hz); 3.37 (t,
1H, H-4); 3.28 (m, 1H, H-5); 2.10 (s, 3H, NHCOCH3); 1.98 (s, 3H,
SeCH3). 13C NMR (CD3OD, 125 MHz): d 177.7 (COCH3); 83.4 (C-5);
80.6 (C-1); 77.5 (C-3); 72.1 (C-4); 63.1 (C-6); 56.7 (C-2), 23.0
(NHCOCH3); 9.6 (SeCH3). 77Se NMR (CD3OD, 95.4 MHz): d207. Anal.
Calcd for C9H17NO5Se: C, 36.25; H, 5.75; N, 4.70. Found: C, 36.77; H,
5.74; N, 4.70. HRMS m/z Calcd for C9H17NO5Se [M+Na]+: 322.016.
Found: 322.016.
From 3 (110 mg, 0.21 mmol), iodomethane (5a, 31 mg, 0.22
mmol) and Et3N (29
l
L, 0.22 mmol), 79 mg (90%), syrup, ½a D22
ꢀ
ꢁ28 (c 0.3, CHCl3); 1H NMR (CDCl3, 500 MHz): d5.20 (t, 1H, H-3);
5.08 (overlapping signals 2H, H-2, H-4); 4.64 (d, 1H, H-1, J1,2
10.1 Hz); 4.24 (dd, 1H, H-6a, J5,6a 4.8 Hz, J6a,6b 12.3 Hz); 4.14 (dd,
1H, H-6b, J5,6b 2.3 Hz); 3.75 (m, 1H, H-5); 2.09, 2.08, 2.05, 2.02,
(s, 12H, 4 ꢂ OCOCH3); 2.00 (SeCH3); 13C NMR (CDCl3, 125 MHz): d
171.0, 170.5, 169.8, 169.1 (COCH3); 77.3 (C-5), 76.8 (C-1), 74.1
(C-3), 70.5 (C-4), 68.6 (C-2), 62.7 (C-6), 21.1, 21.0, 20.9 (OCOCH3);
2.6 (SeCH3); 77Se NMR (CDCl3, 95.4 MHz): d320. Anal. Calcd for
C
15H22O9Se: C, 42.35; H, 5.17. Found. C, 42.22; H, 5.41. HRMS m/z
3.2.9. Ethyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-glucopyranoside
Calcd for: C15H22O9Se [M+K]+: 465.006. Found: 465.020.
(10)38,30,41
From
3
(110 mg, 0.21 mmol), iodoethane (5b, 31 mg,
0.22 mmol) and Et3N (29 lL, 0.22 mmol), 81 mg (90%), syrup,
3.2.6. Methyl 1-seleno-b-D-glucopyranoside (7)
a 2D2
ꢀ
ꢁ49 (c 0.1, CHCl3), lit.38 ꢁ46 (c 5.0, CHCl3); 1H NMR (CDCl3,
From 6 (70 mg, 0.16 mmol), 38 mg (89%), syrup, ½a D22
ꢀ
ꢁ22 (c
½
0.05, CH3OH); 1H NMR (CD3OD, 500 MHz): d 5.20 (t, 1H, H-3);
500 MHz): d5.20 (t, 1H, H-2); 5.14–5.09 (overlapping signals, 2H,

A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
13
H-3, H-4); 4.73 (d, 1H, H-1, J1,2 10.1 Hz); 4.28 (dd, 1H, H-6a, J5,6a
3.2.14. 2-Phenylethyl-1-seleno-b-D-glucopyranoside (15)
4.8 Hz, J6a,6b 12.3 Hz); 4.14 (dd, 1H, H-6b, J5,6b 2.3 Hz); 3.68 (m,
1H, H-5); 2.75 (m, 2H, SeCH2); 2.06, 2.04, 2.01, 2.00 (s, 12H,
4 ꢂ OCOCH3); 1.41 (t, 3H, CH3); 13C NMR (CDCl3, 125 MHz): d
173.7, 173.2, 172.5 (COCH3); 79.8 (C-5), 77.1 (C-1), 76.7 (C-3),
73.1 (C-4), 71.3 (C-2), 65.2 (C-6), 23.8, 23.6, 23.6 (OCOCH3); 17.4
(SeCH2), 16.6 (CH3); 77Se NMR (CDCl3, 95.4 MHz): d 320, lit.30
320.3. HRMS m/z Calcd for: C16H24O9Se [M+Na]+: 463.048. Found:
463.046.
From 14 (100 mg, 0.19 mmol), 59 mg (88%), syrup, ½a D22
ꢀ
ꢁ30 (c
0.1, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.26–7.13 (m, 5H,
Aryl-H); 4.64 (d, 1H, H-1, J1,2 8.7 Hz); 3.89 (dd, 1H, H-6a, J5,6a
5.5 Hz, J6a,6b 12.0 Hz); 3.56 (dd, 1H, H-6b, J5,6b 4.9 Hz); 3.40–3.28
(overlapping signals, 3H, H-2, H-3, H-4); 3.15 (m, 1H, H-5); 3.10–
2.90 (m, 4H, CH2CH2). 13C NMR (CD3OD, 125 MHz): d 142.9 (Cqv.);
129.5 (Aryl-C); 129.3 (Aryl-C); 82.6 (C-5); 81.6 (C-1); 79.6 (C-3);
75.6 (C-2); 71.4 (C-4); 63.0 (C-6); 38.5 (CH2); 24.6 (CH2); 77Se
NMR (CD3OD, 95.4 MHz): d375. HRMS m/z Calcd for C14H20NO5Se
[M+Na]+: 371.037. Found: 371.037.
3.2.10. Ethyl 1-seleno-b-D-glucopyranoside (11)
From 10 (85 mg, 0.19 mmol), 46 mg (87%), syrup, ½a D22
ꢁ29 (c
ꢀ
0.1, CH3OH); 1H NMR (CD3OD, 500 MHz): 4.67 (d, 1H, H-1, J1,2
9.3 Hz); 3.86 (dd, 1H, H-6b, J5,6b 2.0 Hz); 3.66 (dd, 1H, H-6a, J5,6a
5.5 Hz, J6a,6b 12.1 Hz); 3.38–3.32 (overlapping signals, 4H, H-2, H-
3, H-4, H-5); 2.73 (m, 2H, SeCH2); 1.41 (t, 3H, CH3); 13CNMR
(CD3OD: 125 MHz): d 83.3 (C-5), 81.8 (C-1), 79.7 (C-3), 75.5 (C-
4), 71.6 (C-2), 63.1 (C-6), 17.3 (SeCH2), 16.5 (CH3). 77Se NMR
(CD3OD, 95.4 MHz): d304. HRMS m/z Calcd for: C8H16O9Se
[M+Na]+: 295.006. Found: 295.001.
3.2.15. 2-Phenylethyl 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-1-
seleno-b-
D-glucopyranoside (16)
From 4 (100 mg, 0.20 mmol), 2-phenylethylbromide (5c, 37 mg,
0.20 mmol) and Et3N (27 lL, 0.20 mmol), 96 mg (91%), white solid,
mp 190–192 °C, ½a D22
ꢀ
ꢁ67 (c 0.1, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.27–7.11 (m, 5H, Aryl-H); 5.30 (d, 1H, NH); 5.02 (t, 1H, H-4);
4.96 (t, 1H, H-3); 4.65 (d, 1H, H-1, J1,2 10.5 Hz); 4.16–4.03 (overlap-
ping signals, 3H, H-6a, H-6b, H-2); 3.50 (m, 1H, H-5); 3.02–2.89 (m,
4H, CH2CH2); 2.03, 1.93, 1.92 (s, 9H, 3x OCOCH3); 1.89 (s, 3H,
NHCOCH3); 13C NMR (CDCl3: 125 MHz): d 171.1, 170.6, 170.0,
169.2 (COCH3); 140.9 (Cqv.); 128.5, 128.4, 126.5 (Aryl-C), 78.7 (C-
1), 77.1 (C-5), 73.7 (C-3), 68.2 (C-4), 62.3 (C-6), 53.2 (C-2), 36.9
(CH2); 24.5 (CH2); 23.2 (NHCOCH3), 20.6, 20.5 (OCOCH3). 77Se
NMR (CDCl3, 95.4 MHz): d 326. Anal. Calcd for C22H29NO8Se: C,
51.36; H, 5.64; N, 2.72. Found: C, 51.52; H, 5.52; N, 2.72. HRMS
m/z Calcd for: C22H29NO8Se [M+Na]+: 538.095. Found: 538.096.
3.2.11. Ethyl 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-1-seleno-
b-
D-glucopyranoside (12)
From (110 mg, 0.23 mmol), iodoethane (5b, 31 mg,
4
0.22 mmol) and Et3N (29 lL, 0.22 mmol), 88 mg (89%), solid, mp
182–184 °C, ½a 2D2
ꢀ
ꢁ49 (c 0.1, CHCl3); 1H NMR (CDCl3, 500 MHz):
d5.46 (d, 1H, NH); 5.15–5.13 (overlapping signals 2H, H-3, H-4);
4.71 (d, 1H, H-1, J1,2 10.1 Hz); 4.31–4.18 (overlapping signals 3H,
H-2, H-6a, H-6b); 3.67 (m, 1H, H-5); 2.79 (m, 2H, CH2); 2.09,
2.05, 2.04 (s, 12H, 4 ꢂ OCOCH3); 1.97 (s, 3H, NHCOCH3); 1.43 (t,
3H, CH3); 13C NMR (CDCl3, 125 MHz): d 171.4, 170.2 (COCH3);
79.1 (C-1), 77.4 (C-5), 74.0 (C-4), 68.6 (C-3), 62.5 (C-2), 54.2 (C-
6), 23.5 (NHCOCH3); 20.9, 20.8 (OCOCH3); 17.7 (CH2), 15.8 (CH3);
77Se NMR (CDCl3, 95.4 MHz): d 326. Anal. Calcd for C16H25O9Se:
C, 43.84; H, 5.75; N, 3.20. Found: C, 43.77; H, 5.76; N, 3.25. HRMS
m/z Calcd for: C16H25O9Se [M+K]+: 478.022. Found: 478.052.
3.2.16. 2-Phenylethyl 2-acetamido-1-seleno-b-D-
glucopyranoside (17)
From 16 (75 mg, 0.15 mmol), 44 mg (78%), syrup, ½a D22
ꢁ30 (c
ꢀ
0.1, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.24–7.15 (m, 5H,
Aryl-H), 4.75 (d, 1H, H-1, J1,2 10.5 Hz), 3.95–3.80 (overlapping sig-
nals, 2H, H-2, H-6a); 3.72 (dd, 1H, H-6b, J5,6b 2.0 Hz, J6a,6b 12.1 Hz);
3.95–3.70 (overlapping signals, 2H, H-3, H-4); 3.26 (m, 1H, H-5);
3.10–2.90 (m, 4H, CH2CH2); 1.96 (s, 3H, NHCOCH3); 13C NMR
(CD3OD, 125 MHz): d 140.7 (Cqv.); 129.6 (Aryl-C); 129.4 (Aryl-C);
127.2 (Aryl-C); 83.4 (C-5); 80.6 (C-1); 77.4 (C-3); 71.8 (C-2); 63.0
(C-4); 57.2 (C-6); 38.1 (CH2); 25.1 (CH2); 23.0 (NHCOCH3); 77Se
NMR (CD3OD, 95.4 MHz): d 299. HRMS m/z Calcd for C16H23NO5Se
[M+Na]+: 412.063. Found: 412.066.
3.2.12. Ethyl 2-acetamido-2-deoxy-1-seleno-b-D-
glucopyranoside (13)
From 12 (90 mg, 0.21 mmol), 49 mg (76%), syrup, ½a D22
ꢁ28 (c
ꢀ
0.1, CH3OH); 1H NMR (CD3OD, 500 MHz): d 4.79 (d, 1H, H-1, J1,2
10.5 Hz); 3.90–3.79 (overlapping signals 2H, H-2, H-4); 3.67 (dd,
1H, H-6a, J5,6a 4.5 Hz, J6a,6b 12.1 Hz); 3.42 (t, 1H, H-3, J3,4 9.7 Hz);
3.59 (dd, 1H, H-6b, J5,6b 2.3 Hz); 3.28 (m, 1H, H-5); 2.77 (m, 2H,
CH2); 1.98 (s, 3H, NHCOCH3); 1.40 (t, 3H, CH3); 13C NMR (CD3OD:
125 MHz): d 173.7 (COCH3); 83.4 (C-5), 80.2 (C-1), 77.1 (C-4),
72.1 (C-3), 63.1 (C-2), 57.2 (C-6), 22.9 (NHCOCH3); 17.6 (CH2),
16.2 (CH3); 77Se NMR (CDCl3, 95.4 MHz): d 320. HRMS m/z Calcd
for: C10H19NO5Se [M+Na]+: 336.032. Found: 336.040.
3.2.17. Benzyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (18)
From
3 (55 mg, 0.10 mmol), benzyl bromide (5d, 18 mg,
0.11 mmol) and Et3N (15
l
l, 0.11 mmol), 36 mg (70%), syrup, ½a D22
ꢀ
ꢁ111 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d 7.37–7.20 (m,
5H, H-Aryl); 5.12–5.01 (overlapping signals 3H, H-3, H-2, H-4);
4.52 (d, 1H, H-1, J
10.2 Hz); 4.25 (dd, 1H, H-6a, J5,6a 5.2 Hz,
1,2
3.2.13. 2-Phenylethyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-
glucopyranoside (14)
D
-
J6a,6b 12.5 Hz); 4.12 (dd, 1H, H-6b, J5,6b 2.3 Hz); 4.00 (dd, 2H,
CH2); 3.60 (m, 1H, H-5); 2.10, 2.03, 2.00, 1.99, (s, 12H, 4 ꢂ COCH3);
13C NMR (CDCl3, 125 MHz): d 170.5, 170.1, 169.4, 169.2 (COCH3);
137.8 (Cqv.); 129.0, 128.5, 127.1 (Aryl-C); 76.9 (C-1); 76.8 (C-5);
73.7 (C-3); 70.5 (C-2); 68.3 (C-4); 62.2 (C-6); 26.6 (CH2); 20.7,
20.6, 20.5 (COCH3); 77Se NMR (CDCl3, 95.4 MHz): d374. Anal. Calcd
for C21H26O9Se: C, 50.19; H, 5.17. Found: C, 50.34; H, 5.10. HRMS
m/z Calcd for: C21H26O9Se [M+Na]+: 525.063. Found: 525.061.
From 3 (55 mg, 0.10 mmol), 2-phenylethyl bromide (5c, 20 mg,
0.11 mmol) and Et3N (15 lL, 0.11 mmol), 32 mg (60%), white solid,
mp 70–72 °C, ½a 2D2
ꢀ
ꢁ13 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d
7.26–7.13 (m, 5H, Aryl-H); 5.10 (t, 1H, H-3); 5.03 (d, 1H, H-2); 5.01
(dd, 1H, H-4); 4.58 (d, 1H, H-1, J1,2 10.1 Hz); 4.17 (dd, 1H, H-6a, J5,6a
5.0 Hz, J6a,6b 12.4 Hz); 4.08 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.65 (m, 1H,
H-5); 3.10–2.90 (overlapping signals, 4H, CH2CH2); 1.99, 1.98, 1.96,
1.94 (s, 12H, 4 ꢂ OCOCH3); 13C NMR (CDCl3, 125 MHz): d 170.6,
170.1, 169.4 (COCH3); 140.8 (Cqv.); 128.5, 128.4, 126.5 (Aryl-C);
77.2 (C-1); 76.7 (C-5); 73.8 (C-3); 70.7 (C-2); 68.3 (C-4); 62.1 (C-
6), 36.9 (CH2); 24.4 (CH2); 20.7, 20.6, 20.5 (COCH3); 77Se NMR
(CDCl3, 95.4 MHz): d298. Anal. Calcd for: C22H28O9Se: C, 51.76; H,
5.49. Found: C, 51.66; H 5.70; HRMS m/z Calcd for: C22H28O9Se
[M+Na]+: 539.079. Found: 539.077.
3.2.18. Benzyl 1-seleno-b-D-glucopyranoside (19)
From 18 (90 mg, 0.18 mmol), 52 mg (87%), syrup, ½a D22
ꢁ111 (c
ꢀ
0.1, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.39 (dd, 2H, Aryl-H);
7.27 (t, 2H, Aryl-H); 7.15 (t, 1H, Aryl-H); 4.48 (d, 1H, H-1, J1,2
10.2 Hz); 4.11 (d, 1H, SeCH2a); 3.93–3.85 (overlapping signals,
2H, SeCH2b, H-6a); 3.96 (dd, 1H, H-6b, J6a,6b 12.3 Hz, J5,6b 5.3 Hz);
3.34 (overlapping signals, 3H, H-2, H-3, H-4); 3.22 (m, 1H, H-5);

14
A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
13C NMR (CD3OD, 125 MHz): d 142.3 (Cqv.); 131.9 (Aryl-C); 129.3
(Aryl-C); 82.8 (C-5); 82.1 (C-1); 81.7 (C-3); 77.3 (C-2); 72.05 (C-
4); 64.1 (C-6); 28.2 (CH2); 77Se NMR (CD3OD, 95.4 MHz): d366.
(CH2); 77Se NMR (CD3OD, 95.4 MHz): d385. HRMS m/z Calcd for
14H17F3O5Se [M+Na]+: 425.009. Found: 425.011.
C
HRMS m/z Calcd for
C
13H18O5Se [M+Na]+: 357.021. Found:
3.2.23. 3-Chlorobenzyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
357.022.
glucopyranoside (24)
From 3 (55 mg, 0.10 mmol), 3-chlorobenzyl bromide (5f, 20 mg,
3.2.19. Benzyl 2-acetamido-2-deoxy-3,4,6,-tri-O-acetyl-1-
seleno-b- -glucopyranoside (20)
From 4 (100 mg, 0.20 mmol), benzyl bromide (5d, 35 mg,
0.11 mmol) and Et3N (15 lL, 0.11 mmol), 49 mg (97%), white solid,
D
mp 62–65 °C, ½a 2D2
ꢀ
ꢁ107 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.24–7.10 (m, 4H, Aryl-H); 5.05 (t, 1H, H-3, J3,4 9.2 Hz); 5.02–5.01
0.20 mmol) and Et3N (27
l
L, 0.20 mmol), 92 mg (90%), yellow solid,
(overlapping signals 2H, H-2, H-4); 4.64 (d, 1H, H-1, J
9.5 Hz);
1,2
mp 193-195 °C, ½a D22
ꢀ
-155 (c 0.1, CHCl3); 1H NMR (CDCl3, 500 MHz):
4.15 (dd, 1H, H-6a, J5,6a 5.1 Hz, J6a,6b 12.3 Hz); 4.08 (dd, 1H, H-6b,
J5,6b 1.9 Hz); 3.91 (dd, 2H, CH2); 3.54 (m, 1H, H-5); 2.04, 1.95,
1.94, 1.94 (s, 12H, 4x COCH3); 13C NMR (CDCl3, 125 MHz): d
170.5, 170.1, 169.4, 169.3 (COCH3); 140.0 (Cqv.); 134.2 (Cqv.);
129.8, 128.9, 127.2 (Aryl-C), 77.2 (C-5); 76.8 (C-1); 73.6 (C-3);
70.7 (C-2); 68.5 (C-4); 62.1 (C-6); 25.9 (CH2), 20.6, 20.4, 20.5
(COCH3); 77Se NMR (CDCl3, 95.4 MHz): d 378. Anal. Calcd for
d 7.24–7.13 (m, 5H, Aryl-H); 5.28 (d, 1H, NH); 5.03 (t, 1H, H-4, J4,5
9.6 Hz); 4.89 (t, 1H, H-3, J3,4 9.7 Hz); 4.40 (d, 1H, H-1, J1,2
10.5 Hz); 4.30 (t, 1H, H-2); 4.25 (dd, 1H, H-6a, J5,6a 5.2 Hz, J6a,6b
12.1 Hz); 4.19 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.56 (dd, 2H, CH2); 3.56
(m, 1H, H-5); 2.13, 2.04, 2.01 (s, 9H, 3 ꢂ OCOCH3), 1.90 (s, 3H,
NHCOCH3). 13C NMR (CDCl3, 500 MHz): d 171.2, 170.6, 169.9,
169.2 COCH3), 138.4 (Cqv), 129.3, 128.5 (Aryl-C); 126.7 (Aryl-C),
78.1 (C-1); 77.2 (C-5); 73.8 (C-3); 68.3 (C-4); 62.4 (C-6); 53.5 (C-
2); 26.5 (CH2); 23.2 (NHCOCH3), 20.7, 20.6, 20.5 (OCOCH3); 77Se
NMR (CDCl3, 95.4 MHz): d 389. Anal. Calcd for C21H27NO8Se: C,
50.40; H, 5.40; N, 2.80. Found: C, 50.45; H, 5.77; N, 2.85. HRMS
m/z Calcd for: C21H27NO8Se [M+Na]+: 524.079. Found: 524.080.
C
21H25ClO9Se: C, 43.40; H, 4.36. Found: C, 42.68; H, 4.37. HRMS
m/z Calcd for: C22H25ClNO9Se [M+Na]+: 559.024. Found: 559.024.
3.2.24. 3-Chlorobenzyl 1-seleno-b-D-glucopyranoside (25)
From 24 (75 mg, 0.14 mmol), 40 mg (78%), syrup, ½a D22
ꢁ137 (c
ꢀ
0.4, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.43 (s, 1H, Aryl-H);
7.45–7.20 (overlapping signals, 2H, Aryl-H); 7.18 (dd, 1H, Aryl-
H); 4.48 (d, 1H, H-1 J1,2 9.8 Hz); 4.12 (d, 1H, CH2a); 3.95–3.85 (over-
lapping signals, 2H, H-6a, CH2b); 3.70 (dd, 1H, H-6b, J5,6b 5.0 Hz);
3.40–3.20 (overlapping signals, 4H, H-3, H-4, H-2, H-5); 13C NMR
(CD3OD, 125 MHz): d 143.4 (Cqv.); 135.2 (Cqv.); 131.0, 130.3
128.7, 127.8 (Aryl-C); 83.5 (C-5); 80.8 (C-1); 79.8 (C-2); 75.5 (C-
3); 71.8 (C-4); 63.1 (C-6); 25.7 (CH2); 77Se NMR (CD3OD,
95.4 MHz): d 374. HRMS m/z Calcd for C13H17ClO5Se [M+Na]+:
390.982. Found: 390.983.
3.2.20. Benzyl 2-acetamido-2-deoxy-1-seleno-b-D-
glucopyranoside (21)
From 20 (80 mg, 0.16 mmol), 53 mg (88%), syrup, ½a D22
ꢁ129 (c
ꢀ
0.1, CH3OH); 1H NMR (CD3OD, 500 MHz): d7.35 (d, 2H, Aryl-H);
7.26 (t, 2H, Aryl-H); 7.14 (t, 1H, Aryl-H); 4.50 (d, 1H, H-1, J1,2
11.1 Hz); 4.06 (d, 1H, SeCH2a); 3.92–3.87 (overlapping signals, 3H,
H-6b, SeCH2b, H-2); 3.70 (dd, 1H, H-6a, J5,6a 5.7 Hz, J6a,6b 12.3 Hz);
3.35–3.28 (overlapping signals, 2H, H-3, H-4); 3.21 (m, 1H, H-5);
1.90 (s, 3H, NHCOCH3); 13C NMR (CD3OD, 125 MHz): d 173.7
(COCH3); 140.65 (Cqv.); 130.4, 129.6, 127.8 (Aryl-C); 83.6 (C-5);
80.1 (C-1); 79.7 (C-4); 77.6 (C-3); 63.3 (C-6); 56.1 (C-2); 26.9
(CH2); 23.0 (NHCOCH3); 77Se NMR (CD3OD, 95.4 MHz): d 380. HRMS
m/z Calcd for C13H17ClO5Se [M+Na]+: 398.048. Found: 398.050.
3.2.25. 4-Bromobenzyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (26)
From
3 (55 mg, 0.10 mmol), 4-bromobenzyl bromide (5g,
18 mg, 0.11 mmol) and Et3N (12 lL, 0.11 mmol), 56 mg (93%), syr-
up, ½a 2D2
ꢀ
ꢁ129 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d 7.35 (dd,
3.2.21. 2-(Trifluoromethyl)benzyl 2,3,4,6-tetra-O-acetyl-1-
2H, Aryl-H), 7.10 (dd, 2H, Aryl-H); 5.14 (t, 1H, H-3); 5.11 (t, 1H, H-
2); 5.08 (t, 1H, H-4); 4.53 (d, 1H, H-1, J 1,2 9.0 Hz); 4.24 (dd, 1H, H-
6a, J5,6a 5.1 Hz, J6a,6b 12.4 Hz); 4.14 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.73
(dd, 2H, CH2); 3.61 (m, 1H, H-5); 2.10, 2.03, 2.01, 1.99 (s, 12H, 4x
OCOCH3); 13C NMR (CDCl3, 125 MHz): d 170.5, 170.1, 169.4;
169.3 (COCH3); 136.9 (Cqv.); 131.6; 130.7 (Aryl-C); 120.9 (Cqv.);
77.2 (C-5); 76.7 (C-1); 73.6 (C-3); 70.5 (C-2); 68.3 (C-4); 62.2 (C-
6), 25.7 (CH2); 20.7, 20.6, 20.5 (COCH3); 77Se NMR (CDCl3,
95.4 MHz): d 376 ppm. Anal. Calcd for C21H25BrO9Se: C, 43.40; H,
4.36. Found: C, 43.04; H, 4.44. HRMS m/z Calcd for: C21H25BrO9Se
[M+Na]+: 602.981. Found: 602.970.
seleno-b-D-glucopyranoside (22)
From 3 (55 mg, 0.10 mmol), 2-(trifluoromethyl)benzyl bromide
(5e, 27 mg, 0.11 mmol) and Et3N (15 lL, 0.11 mmol), 55 mg (95%),
syrup, ½a 2D2
ꢀ
ꢁ31 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d 7.55–
7.27 (m, 4H, Aryl-H); 5.25–5.10 (overlapping signals, 3H, H-3, H-2,
H-4); 4.72 (d, 1H, H-1, J1,2 9.0 Hz); 4.26 (dd, 1H, H-6a, J5,6a 4.9 Hz,
J6a,6b 12.5 Hz); 4.21 (dd, 1H, H-6b, J5,6b 2.0 Hz); 4.12 (dd, 2H,
CH2); 3.70 (m, 1H, H-5), 2.13, 2.10, 2.03, 2.00 (s, 12H, 4 ꢂ OCOCH3);
13C NMR (CDCl3, 125 MHz): d 170.6, 170.1, 169.4, 169.3 (COCH3);
137.2 (Cqv.); 132.2, 131.9, 128.1, 126.2 (Aryl-C); 127.2 (CF3); 77.4
(C-1); 77.2 (C-5); 73.6 (C-3); 70.6 (C-2); 68.3 (C-4); 62.1 (C-6),
29.6 (CH2); 20.6, 20.6, 20.5 (COCH3); 77Se NMR (CDCl3,
95.4 MHz): d 388 ppm. Anal. Calcd for: C22H25F3O9Se: C, 46.31; H,
4.38. Found: C, 46.31; H, 4.86. HRMS m/z Calcd for: C22H25F3O9Se
[M+Na]+: 593.062. Found: 593.048.
3.2.26. 4-Bromobenzyl 1-seleno-b-D-glucopyranoside (27)
From 26 (80 mg, 0.14 mmol), 53 mg (94%), syrup, ½a D22
ꢁ119 (c
ꢀ
0.4, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.43 (dd, 2H, Aryl-H);
7.30 (dd, 2H, Aryl-H); 4.45 (d, 1H, H-1, J1,2 9.8 Hz); 4.09 (d, 1H, Se-
CH2a); 3.91 (dd, 1H, H-6a, J5,6a 6.2 Hz, J6a,6b 11.8 Hz); 3.84 (d, 1H,
SeCH2b); 3.68 (dd, 1H, H-6b, J5,6b 5.0 Hz); 3.40–3.20 (overlapping
signals, 3H, H-4, H-2, H-3); 3.18 (m, 1H, H-5); 13C NMR (CD3OD,
125 MHz): d 140.4 (Cqv.); 132.6, 130.0 (Aryl-C); 121.4 (Cqv.); 83.5
(C-5); 80.6 (C-1); 79.8 (C-3); 75.5 (C-4); 71.8 (C-2); 63.2 (C-6);
25.6 (CH2); 77Se NMR (CD3OD, 95.4 MHz): d374. HRMS m/z Calcd
for: C13H17BrO5Se [M+Na] +: 434.932. Found: 434.934.
3.2.22. 2-(Trifluoromethyl)benzyl 1-seleno-b-D-glucopyranoside
(23)
From 22 (70 mg, 0.12 mmol), 45 mg (92%), syrup, ½a D22
ꢁ134 (c
ꢀ
0.2, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.63 (d, 2H, Aryl-H);
7.58 (t, 1H, Aryl-H); 7.37 (t, 1H, Aryl-H); 4.71 (d, 1H, H-1, J1,2
9.2 Hz); 4.26 (d, 1H, SeCH2a); 4.09 (d, 1H, SeCH2b); 3.72 (dd, 1H,
H-6a, J5,6a 5.3 Hz, J6a,6b 12.1 Hz); 4.21 (dd, 1H, H-6b, J5,6b 6.0 Hz);
3.28 (overlapping signals, 4H, H-2, H-3, H-4, H-5). 13C NMR
(CD3OD, 125 MHz): d 140.2 (Cqv); 133.8, 133.4 (Aryl-C); 129.1
(Cqv.); 128.2, 127.2 (Aryl-C); 127.1 (CF3); 125.1 (Cqv); 83.5 (C-5);
81.4 (C-1); 79.9 (C-3); 75.7 (C-2); 71.7 (C-4); 63.1 (C-6); 22.8
3.2.27. 4-Cyanobenzyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (28)
From 3 (55 mg, 0.10 mmol), 4-cyanobenzyl bromide (5h, 21 mg,
0.11 mmol) and Et3N (15 L, 0.11 mmol), 50 mg (92%), white solid,
l

A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
15
mp 80–81 °C, ½a 2D2
ꢀ
ꢁ80 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d
d8.09 (dd, 2H, Aryl-H, Jo 8.57 Hz); 7.41 (dd, 2H, Aryl-H); 5.09 (t, 1H,
H-2); 5.06 (t, 1H, H-4); 4.61 (d, 1H, H-1, J1,2 9.1 Hz); 5.02 (t, 1H, H-
3, J3,4 9.5 Hz); 4.18 (dd, 1H, H-6a, J5,6a 5.1 Hz, J6a,6b 12.3 Hz); 4.08
(dd, 1H, H-6b, J5,6b 2.2 Hz); 3.05 (d, 2H, CH2); 3.59 (m, 1H, H-5);
2.04, 1.96, 1.94, 1.93 (s, 12H, 4 ꢂ OCOCH3); 13C NMR (CDCl3,
125 MHz): d 170.4, 170.0, 169.4, 169.2 (COCH3); 146.05 (Cqv.);
145.9 (Cqv); 129.8, 123.8 (Aryl-C); 77.2 (C-5); 76.7 (C-1); 73.4 (C-
2); 70.4 (C-4); 68.2 (C-3); 62.1 (C-6), 25.2 (CH2); 20.7, 20.6, 20.5
(COCH3); 77Se NMR (CDCl3, 95.4 MHz): d 383 ppm. Anal. Calcd
for: C21H25NO11Se: C, 46.06; H, 4.57; N, 2.55. Found: C, 46.52; H,
7.61 (dd, 2H, Aryl-H), 7.41 (dd, 2H, Aryl-H); 5.18 (t, 1H, H-3); 5.15–
5.02 (overlapping signals 2H, H-2, H-4); 4.58 (d, 1H, H-1, J1,2
9.8 Hz); 4.24 (dd, 1H, H-6a, J6a,6b 12.4 Hz, J5,6a 5.0 Hz); 4.14 (dd,
1H, H-6b, J5,6b 2.2 Hz); 3.99 (dd, 2H, CH2); 3.64 (m, 1H, H-5);
2.10, 2.02, 2.00, 1.96 (s, 12H, 4 ꢂ COCH3); 13C NMR (CDCl3,
125 MHz): d 170.4, 170.0, 169.5, 169.4 (COCH3); 143.8 (Cqv.);
134.3, 129.8 (Aryl-C); 118.6 (CN); 110.8 (Cqv-CN.); 77.0 (C-5);
76.7 (C-1); 73.5 (C-3); 70.4 (C-2); 68.2 (C-4); 62.1 (C-6); 25.7
(CH2), 20.7, 20.6, 20.5 (COCH3); 77Se NMR (CDCl3, 95.4 MHz): d
379 ppm. Anal. Calcd for C22H25NO9Se: C, 50.09; H, 4.74; N, 2.60.
Found: C, 48.40; H, 4.76; N, 2.50. HRMS m/z Calcd for: C22H25NO9Se
[M+Na]+: 550.059. Found: 550.065.
4.06; N, 2.40; HRMS m/z Calcd for:
570.049. Found: 570.049.
C
21H25NO11Se [M+Na]+:
3.2.32. 4-Nitrobenzyl 2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-1-
seleno-b- -glucopyranoside (33)
From 4 (100 mg, 0.20 mmol), 4-nitrobenzyl chloride (5i, 44 mg,
3.2.28. 4-Cyanobenzyl 1-seleno-b-
D
-glucopyranoside (29)
D
From 28 (75 mg, 0.14 mmol), 50 mg (96%), syrup, ½a D22
ꢁ28 (c
ꢀ
0.3, CH3OH); 1H NMR (CD3OD, 500 MHz: d 7.25 (dd, 2H, Aryl-H);
7.15 (dd, 2H, Aryl-H); 4.52 (d, 1H, H-1, J1,2 9.6 Hz); 4.24 (d, 1H,
CH2a); 4.02 (d, 1H, CH2b); 3.98 (dd, 1H, H-6b, J5,6b 2.07 Hz); 3.75
(dd, 1H, H-6a, J5,6a 6.2 Hz, J6a,6b 12.0 Hz); 3.56–3.30 (overlapping
signals, 3H, H-3, H-2, H-4); 3.25 (m, 1H, H-5); 13C NMR (CD3OD,
125 MHz): d 147.5 (Cqv.); 133.4, 131.3 (Aryl-C); 119.9 (CN), 111.3
(Cqv-CN); 83.6 (C-5); 80.9 (C-1); 80.5 (C-2); 75.5 (C-4); 71.8 (C-
3); 63.2 (C-6); 25.7 (CH2); 77Se NMR (CD3OD, 95.4 MHz): d 384.
HRMS m/z Calcd for C14H17NO5Se [M+Na]+: 382.016. Found:
382.036.
0.20 mmol) and Et3N (27
l
L, 0.20 mmol), 96 mg (86%), light pink
solid, mp 213–215 °C, ½a D22
ꢀ
ꢁ143 (c 0.1, CHCl3); 1H NMR (CDCl3,
500 MHz): d8.16 (dd, 2H, Aryl-H); 7.48 (dd, 2H, Aryl-H); 5.46 (d,
1H, NH); 5.13 (t, 1H, H-4, J4,5 9.6 Hz); 5.02 (t, 1H, H-3, J3,4
9.8 Hz); 4.56 (d, 1H, H-1 J1,2 10.5 Hz); 4.24 (d, 1H, H-2, J2,3
5.2 Hz); 4.25 (dd, 1H, H-6a, J6a,6b 13.0 Hz, J5,6a 5.1 Hz); 4.18 (dd,
1H, H-6b, J5,6b 1.9 Hz); 4.05 (dd, 2H, CH2); 3.60 (m, 1H, H-5),
2.12, 2.04, 1.93 (s, 9H, 3 ꢂ OCOCH3); 1.90 (s, 3H, NHCOCH3); 13C
NMR (CDCl3, 500 MHz): d171.3, 170.5, 170.1, 169.2 (COCH3);
146.5 Cqv.); 129.5, 123.5 Aryl-C); 77.8 (C-1); 76.9 (C-5); 73.2 (C-
3); 67.8 (C-4); 62.03 (C-6); 53.2 (C-2); 24.9 (CH2); 23.2 (NHCOCH3);
20.8, 20.6, 20.5 (OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d399.
HRMS m/z Calcd for: C21H26N2O10Se [M+Na]+: 569.075. Found:
569.065.
3.2.29. 4-Cyanobenzyl 2-acetamido-2-deoxy-3,4,6,-tri-O-acetyl-
1-seleno-b-
D-glucopyranoside (30)
From 4 (100 mg, 0.20 mmol), 4-cyanobenzyl bromide (5h,
39 mg, 0.20 mmol) and Et3N (27 lL, 0.20 mmol), 102 mg (95%),
light yellow solid, mp 98–100 °C, ½a D22
ꢀ
ꢁ136 (c 0.1, CHCl3); 1H
3.2.33. 4-Methoxybenzyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
NMR (CDCl3, 500 MHz): d 7.60 (dd, 2H, Aryl-H); 7.45 (dd, 2H,
Aryl-H); 5.59 (d, 1H, NH); 5.09 (d, 1H, H-3); 5.02 (t, 1H, H-4);
4.55 (d, 1H, H-1, J1,2 10.5 Hz); 4.26 (d, 1H, H-2); 4.23 (dd, 1H, H-
6a, J5,6a 5.1 Hz, J6a,6b 10.1 Hz); 4.16 (dd, 1H, H-6b, J5,6b 2.2 Hz);
3.95 (dd, 2H, CH2); 3.59 (m, 1H, H-5); 2.10, 2.04, 2.03, (s, 9H,
3 ꢂ OCOCH3); 1.91 (s, 3H, NHCOCH3); 13C NMR (CDCl3, 500 MHz):
d 171.2, 170.4, 170.1, 169.2 COCH3), 144.3 (Cqv.); 132.3, 129.8
(Aryl-C), 118.7 (CN); 110.7 (Cqv.-CN); 78.4 (C-1), 78.3 (C-5); 73.6
(C-3), 68.3 (C-4), 62.4 (C-6), 53.7 (C-2), 25.6 (CH2); 23.2
(NHCOCH3); 20.7, 20.6, 20.5 (OCOCH3); 77Se NMR (CDCl3,
95.4 MHz): d393. Anal. Calcd for C22H26N2O8Se: C, 50.19; H, 4.94;
N, 5.32. Found: C, 50.57; H, 4.93; N, 5.32. HRMS m/z Calcd for:
glucopyranoside (34)30
From 3 (55 mg, 0.10 mmol), 4-methoxybenzyl bromide (5j,
22 mg, 0.11 mmol) and Et3N (15 lL, 0.11 mmol), 36 mg (65%), syr-
up, ½a 2D2
ꢀ
ꢁ111 (c 1.6, CHCl3); lit.30 ꢁ13.5 (c 0.7, CHCl3); 1H NMR
(CDCl3, 500 MHz): d 7.23 (dd, 2H, Aryl-H); 6.83 (dd, 2H, Aryl-H);
5.20–5.05 (overlapping signals, 3H, H-3, H-2, H-4); 4.50 (d, 1H,
H-1, J1,2 9.9 Hz); 4.25 (dd, 1H, H-6a, J5,6a 4.8 Hz, J6a,6b 12.3 Hz);
4.15 (dd, 1H, H-6b, J5,6b 1.1 Hz); 3.95 (dd, 2H, CH2); 3.81 (s, 3H,
OCH3); 3.59 (m, 1H, H-5); 2.11, 2.0, 2.01, 2.00 (s, 12H,
4 ꢂ OCOCH3); 13C NMR (CDCl3, 125 MHz): d 170.5, 170.1, 169.4,
169.3 (COCH3); 158.7 (Cqv); 130.1, 113.9 (Aryl-C); 129.5 (Cqv.);
76.8 (C-5); 76.7 (C-1); 73.7 (C-4); 70.5 (C-2); 68.3 (C-3); 62.3 (C-
6); 55.0 (COCH3); 26.3 (CH2); 21.1, 20.6 (4 ꢂ COCH3); 77Se NMR
C
22H26N2O8Se [M+Na]+: 549.075. Found: 549.077.
(CDCl3, 95.4 MHz):
22H28O10Se: C, 49.60; H, 5.26. Found: C, 50.85; H, 5.75; HRMS
m/z Calcd for: C22H28O10Se [M+Na]+: 555.074. Found: 555.075.
d
373 ppm, lit.30 373.3. Anal. Calcd for
3.2.30. 4-Cyanobenzyl 2-acetamido-2-deoxy-1-seleno-b-
D-
C
glucopyranoside (31)
From 30 (75 mg, 0.14 mmol), 49 mg (86%), syrup, ½a D22
ꢁ117 (c
ꢀ
1.6 CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.75 (t, 1H, Aryl-H);
7.26 (dd, 2H, Aryl-H); 4.60 (d, 1H, H-1, J1,2 9.3 Hz); 4.30 (d, 1H,
CH2a); 4.10–3.90 (overlapping signals, 3H, H-2, CH2b, H-6a); 3.78
(1H, dd, H-6b, J6a,6b 10.0 Hz, J5,6b 2.1 Hz); 3.50–3.35 (overlapping
signals, 2H, H-3, H-4); 3.30 (m, 1H, H-5); 2.05 (s, 3H, NHCOCH3).
13C NMR (CD3OD, 125 MHz): d 173.6 (COCH3); 144.2 (Cqv.), 133.4
(Aryl-C); 130.4 (Aryl-C); 119.9 (CN); 111.4 (Cqv.-CN); 83.7 (C-5);
79.7 (C-1); 77.4 (C-4); 72.3 (C-3); 63.2 (C-6); 56.8 (C-2), 26.1
(CH2); 22.8 (NHCOCH3); 77Se NMR (CD3OD, 95.4 MHz): d 397.
HRMS m/z Calcd for C14H17NO5Se [M+Na]+: 423.043. Found:
423.045.
3.2.34. 4-Methoxybenzyl 1-seleno-b-D-glucopyranoside (35)
From 34 (40 mg, 0.08 mmol), 24 mg (86%), syrup, ½a D22
ꢁ137 (c
ꢀ
0.2, CH3OH); 1H NMR (CD3OD, 500 MHz: d 7.35 (dd, 2H, Aryl-H);
6.95 (dd, 2H, Aryl-H); 4.53 (d, 1H, H-1, J1,2 9.6 Hz); 4.10 (d, 1H,
CH2a); 3.98–3.80 (overlapping signals, 2H, H-6b, CH2b); 3.86 (s,
3H, OCH3); 3.75 (dd, 1H, H-6a, J5,6a 5.6 Hz, J6a,6b 11.6 Hz); 3.42–
3.30 (overlapping signals, 3H, H-3, H-2, H-4); 3.24 (m, 1H, H-5);
13C NMR (CD3OD, 125 MHz): d 160.1 (Cqv.); 134.1, 132.5 (Cqv.);
131.5, 131.0 (Aryl-C); 83.4 (C-5); 81.4 (C-1); 80.7 (C-2); 75.4 (C-
4); 71.8 (C-3); 63.2 (C-6); 55.9 (OCH3); 26.3 (CH2). 77Se NMR
(CD3OD, 95.4 MHz):
d 364. HRMS m/z Calcd for C14H20O6Se
[M+Na]+: 387.032. Found: 387.032.
3.2.31. 4-Nitrobenzyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (32)
3.2.35. Phenyl 2,3,4,6-tetra-O-acetyl-1-seleno-b-D-
From 3 (55 mg, 0.10 mmol), 4-nitrobenzyl chloride (5i, 22 mg,
glucopyranoside (36)19
0.11 mmol) and Et3N (15
l
L, 0.11 mmol), 55 mg (98%), white solid
From
3
(55 mg, 0.10 mmol), bromobenzene (5k, 32 mg,
L, 0.25 mmol), 24 mg (49%), solid, mp
mp 75–77 °C, ½a 2D2
ꢀ
ꢁ122 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz):
0.20 mmol) and Et3N (33 l

16
A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
97–98 °C, lit.19 98 °C, ½a D22
ꢀ
ꢁ26 (c 0.15, CHCl3); lit.19 ꢁ25 (c 0.1,
170.3, 169.9, 169.8 (COCH3); 162.9 (Cqv); 145.1 (Aryl-C); 142.4
(Cqv); 130.7, 125.1 (Aryl-C); 80.7 (C-1); 75.9 (C-5); 71.6 (C-4);
67.2 (C-3); 67.1 (C-2); 61.3 (C-6), 20.7, 20.6, 20.5 (OCOCH3); 77Se
NMR (CDCl3, 95.4 MHz): d495. Anal. Calcd for C19H22N2O11Se: C,
51.76; H, 5.49. Found: C, 51.66; H 5.70. HRMS m/z Calcd for:
CH2Cl2); 1H NMR (CDCl3, 500 MHz): d 7.62 (d, 2H, Aryl-H); 7.42–
7.32 (m, 3H, Aryl-H); 5.20 (t, 1H, H-2, J2,3 9.2 Hz); 5.05 (t, 1H, H-
3, J3,4 9.8 Hz); 5.02 (t, 1H, H-4, J4,5 9.3 Hz); 4.90 (d, 1H, H-1, J1,2
10.2 Hz); 4.22–4.16 (overlapping signals, 2H, H-6a, H-6b); 3.71
(m, 1H, H-5); 2.10, 2.08, 2.06 (s, 12H, 4 ꢂ OCOCH3); 13C NMR
(CDCl3, 125 MHz): d 170.5, 170.2, 169.4, 169.3 (COCH3); 135.3,
129.0, 128.6 (Aryl-C); 126.9 (Cqv.); 80.9 (C-1); 76.9 (C-5); 73.8 (C-
2); 70.7 (C-3); 68.1 (C-4); 62.1 (C-6), 20.8, 20.7, 20.6 (COCH3);
77Se NMR (CDCl3, 95.4 MHz): d 420. Anal. Calcd for C20H24O9Se:
C, 49.30; H, 4.96. Found: C, 49.35; H, 5.13. HRMS m/z Calcd for
C
19H22N2O11Se [M+Na]+: 557.039. Found: 557.031.
3.2.40. (5-Nitropyrid-2-yl) 2-acetamido-2-deoxy-3,4,6-tri-O-
acetyl-1-seleno-b- -glucopyanoside (41)
From 4 (100 mg, 0.20 mmol), 2-chloro-5-nitropyridine (5m,
D
33 mg, 0.20 mmol) and Et3N (29 lL, 0.22 mmol), 95 mg (87%), so-
C
20H24O9Se [M+Na]+: 511.048. Found: 511.048.
lid, mp 197–199 °C, ½a D22
ꢀ
ꢁ2 (c 0.2, CDCl3); 1H NMR (CDCl3,
500 MHz): d 9.24 (d, 1H, Aryl-H); 8.24 (dd, 1H, Aryl-H); 7.51 (dd,
1H, Aryl-H); 6.02 (dd, 1H, NH); 5.88 (dd, 1H, H-1, J1,2 10.8 Hz);
5.21 (overlapping signals, 2H, H-3, H-4); 4.49 (m, 1H, H-2); 4.26
(dd, 1H, H-6a, J5,6a 2.0 Hz, J6a,6b 12.5 Hz); 4.05 (d, 1H, H-6b, J5,6b
1.8 Hz); 3.83 (m, 1H, H-5); 2.05, 2.03, 2.01 (s, 9H, 3 ꢂ OCOCH3);
1.89 (s, 3H, NHCOCH3); 13C NMR (CDCl3, 125 MHz): d 171.3,
170.5, 170.3, 169.2 (COCH3); 163.9 (Cqv); 145.7 (Aryl-C); 142.3
(Cqv); 130.5, 125.3 (Aryl-C); 81.8 (C-1); 77.5 (C-5); 73.8 (C-4);
67.9 (C-3); 61.9 (C-6); 53.3 (C-2), 23.1 (NHCOCH3); 20.6, 20.5
(OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d 503. Anal. Calcd for
C19H23N3O10Se: C, 42.80; H, 4.32; N, 7.89. Found C, 43.51; H,
4.37; N, 7.87. HRMS m/z Calcd for: C19H23N3O10Se [M+Na]+:
556.050. Found: 556.047.
3.2.36. Phenyl 1-seleno-b-D-glucopyranoside (37)
From 36 (50 mg, 0.10 mmol), 27 mg (83%), syrup, ½a D22
ꢁ137 (c
ꢀ
0.4, CH3OH); 1H NMR (CD3OD, 500 MHz): d 7.70 (m, 2H, Aryl-H);
7.45–7.37 (m, 3H, Aryl-H); 4.80 (d, 1H, H-1, J1,2 9.4 Hz); 3.87 (dd,
1H, H-6a, J5,6a 4.9 Hz, J6a,6b 12.3 Hz); 3.65 (dd, 1H, H-6b, J5,6b
2.5 Hz); 3.40–3.23 (overlapping signals, 4H, H-2, H-3, H4, H-5);
13C NMR (CD3OD: 125 MHz): d 134.6 Aryl-C); 131.0 (Cqv.); 129.1
(Aryl-C); 127.9 (Aryl-C); 85.3 (C-1), 82.4 (C-5), 78.9 (C-3), 73.7
(C-4), 70.6 (C-2), 62.2 (C-6); 77Se NMR (CD3OD, 95.4 MHz): d 404.
HRMS m/z Calcd for C12H16O5Se [M+Na]+: 343.005. Found:
343.006.
3.2.37. 2,4-Dinitrophenyl 2,3,4,6,-tetra-O-acetyl-1-seleno-b-D-
glucopyranoside (38)38
3.2.41. 1-Se-Acetyl-2,3,4,6-tetra-O-acetyl-b-D-glucopyranose
From 3 (55 mg, 0.10 mmol), 2,4-dinitrophenyl bromide (5l,
(42)
22 mg, 0.11 mmol) and Et3N (15
l
L, 0.11 mmol), 38 mg (64%),
From 3 (55 mg, 0.10 mmol), acetic anhydride (5n, 26 lL,
white solid, mp 190–193 °C, lit.38 192–194 °C, ½a D22
ꢀ
ꢁ13 (c 1.6,
0.25 mmol) and Et3N (40 lL, 0.30 mmol), 26 mg (55%), syrup,
CHCl3), lit.38 ꢁ100 (c 5.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d
9.11 (s, 1H, Aryl-H); 8.38 (dd, 1H, Aryl-H); 8.03 (dd, 1H, Aryl-H);
5.34 (t, 1H, H-2); 5.27 (t, 1H, H-3, J3,4 9.0 Hz); 5.19 (t, 1H, H-4,
J4,5 8.5 Hz); 5.17 (d, 1H, H-1, J1,2 9.2 Hz); 4.27 (dd, 1H H-6a, J5,6a
5.6 Hz, J6a,6b 12.5 Hz); 4.21 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.91 (m,
1H, H-5); 2.12, 2.08, 2.06 (s, 12H, 4 ꢂ OCOCH3); 13C NMR (CDCl3,
125 MHz): d 169.9, 169.2 (COCH3); 145.9 (Cqv.); 140.4 (Cqv.);
131.1, 127.0, 121.3 (Aryl-C); 79.6 (C-1); 77.4 (C-5); 73.4 (C-2);
69.5 (C-3); 68.0 (C-4); 62.2 (C-6), 20.6, 20.5 (COCH3); 77Se NMR
(CDCl3, 95.4 MHz): d496. Anal. Calcd for C20H22N3O12Se: C, 41.50;
H, 3.80; N, 4.50. Found: C, 41.31; H, 3.81; N, 4.51. HRMS m/z Calcd
for C20H22N2O13Se [M+Na]+: 601.018. Found: 601.020.
½
a 2D2
ꢀ
ꢁ4 (c 1.6, CHCl3); 1H NMR (CDCl3, 500 MHz): d 5.28 (d, 1H,
H-1, J1,2 9.4 Hz); 5.23 (t, 1H, H-3); 5.19 (t, 1H, H-2); 5.12 (t, 1H,
H-4); 4.26 (dd, 1H, H-6a, J6a,6b 12.5 Hz, J5,6a 4.5 Hz); 4.11 (dd, 1H,
H-6b, J5,6b 2.0 Hz); 3.81 (m, 1H, H-5); 2.45 (s, 3H, SeCOCH3); 2.08,
2.03, 2.01, 2.00 (s, 12H, 4 ꢂ OCOCH3); 13C NMR (CDCl3,
125 MHz): d 194.3 (SeCOCH3); 170.5, 169.8, 169.2 (OCOCH3);
79.9 (C-1); 77.3 (C-5); 73.8 (C-3); 69.8 (C-2); 67.9 (C-4); 61.7 (C-
6); 34.7 (SeCOCH3); 20.6, 20.5, 20.4 (OCOCH3); 77Se NMR (CDCl3,
95.4 MHz): d 662. Anal. Calcd for: C16H22O10Se: C, 42.29; H, 4.84.
Found C, 42.43; H 4.06.
3.2.42. 1-Se-acetyl-2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-b-
D-
glucopyranose (43)
3.2.38. 2,4-Dinitrophenyl 1-seleno-b-
D
-glucopyranoside (39)
From 4 (100 mg, 0.21 mmol), acetic anhydride (5n, 52 lL,
From 38 (90 mg, 0.16 mmol), 55 mg (86%), syrup, ½a D22
ꢀ
ꢁ18 (c
0.50 mmol) and Et3N (53 lL, 0.40 mmol), 82 mg (89%), light pink
1.6, CD3OD); 1H NMR (CD3OD, 500 MHz): d 9.10 (s, 1H, Aryl-H);
8.42 (dd, 1H, Aryl-H); 8.25 (dd, 1H, Aryl-H); 5.24 (t, 1H, H-1, J2,3
10.0 Hz); 5.27 (t, 1H, H-3, J3,4 9.0 Hz); 5.19 (t, 1H, H-4, J4,5
8.5 Hz); 5.17 (d, 1H, H-1); 4.27 (dd, 1H, H-6a, J5,6a 5.6 Hz, J6a,6b
12.5 Hz); 4.21 (dd, 1H, H-6b, J5,6b 2.2 Hz); 3.91 (m, 1H, H-5); 13C
NMR (CDCl3, 125 MHz): d 155.8, 155.3, 148.9 (Cqv); 141.3, 137.3,
131.0 (Aryl-C); 87.5 (C-1); 85.4 (C-5); 82.4 (C-4); 79.1 (C-3); 77.5
(C-6); 71.6 (C-2); 77Se NMR (CD3OD, 95.4 MHz): d404. HRMS m/z
Calcd for C12H14N2O9Se [M+Na]+:432.975. Found: 432.978.
solid, mp 186–188 °C, ½a D22
ꢀ
ꢁ21 (c 1.6, CHCl3); 1H NMR (CDCl3,
500 MHz): d 5.60 (d, 1H, NH), 5.18 (overlapping signals H-1, H-
3); 5.08 (t, 1H, H-4); 4.48 (t, 1H, H-2); 4.26 (dd, H-6a, J5,6a 9.2 Hz,
J6a,6b 12.2 Hz); 4.11 (d, H-6b, J5,6b 3.0 Hz); 3.70 (m, 1H, H-5); 2.45
(s, 3H, SeCOCH3); 2.09, 2.05, 2.03 (s, 3H, 4x COCH3); 13C NMR
(CDCl3, 500 MHz): d 194.5 (SeCOCH3); 171.3, 170.6, 169.9, 169.2
COCH3); 81.6 (C-1); 77.5 (C-5); 74.1 (C-3); 67.7 (C-4); 61.8 (C-6);
53.2 (C-2); 34.7 (SeCOCH3); 23.1 (NHCOCH3); 20.7, 20.6, 20.5
(OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d 673. Anal. Calcd for
C16H23NO9Se: C, 42.48; H, 5.09; N, 3.10. Found: C, 42.95; H, 5.06;
3.2.39. (5-Nitropyrid-2-yl) 2,3,4,6-tetra-O-acetyl-1-seleno-b-
D
-
N, 3.13.
glucopyranoside (40)38
From 3 (100 mg, 0.19 mmol), 2-chloro-5-nitropyridine (5m,
3.2.43. 1-Se-Benzoyl-2,3,4,6-tetra-O-acetyl-b-D-glucopyranose
33 mg, 0.22 mmol) and Et3N (29
l
L, 0.22 mmol), 88 mg (88%), so-
(44)
lid, mp 178–179 °C, lit.38 176–178 °C, ½a D22
ꢀ
ꢁ26 (c 0.2, CHCl3),
From 3 (55 mg, 0.10 mmol), benzoyl chloride (5o, 15 mg,
lit.38 ꢁ4 (c 5.0, CHCl3); 1H NMR (CDCl3, 500 MHz): d 9.29 (s, 1H,
Aryl-H); 8.27 (dd, 1H, Aryl-H); 7.50 (dd, 1H, Aryl-H); 5.90 (d, H-
1, J1,2 10.0 Hz); 5.51 (overlapping signals, 2H, H-4, H-3); 4.13 (m,
1H, H-4); 4.23 (dd, 1H, H-6a, J5,6a 2.0 Hz, J6a,6b 12.2 Hz); 4.10 (dd,
1H, H-6b, J5,6b 2.1 Hz); 3.75 (m, 1H, H-5); 2.20, 2.10, 2.05, 1.95 (s,
12H, 4x OCOCH3); 13C NMR (CDCl3, 125 MHz): d 170.3, 170.1,
0.20 mmol) and Et3N (27 lL, 0.11 mmol), 32 mg (60%), white solid,
mp 190–192 °C, ½a D22
ꢀ
ꢁ13 (c 0.1, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.84 (d, 1H, Aryl-H), 7.61 (t, 1H, Ar-H); 7.46 (t, 2H, Aryl-H); 5.53
(d, 1H, H-1, J1,2 10.3 Hz); 5.45-5.30 (overlapping signals 2H, H-2, H-
3); 5.18 (t, 1H, H-4, J3,4 10.1 Hz); 4.31 (dd, 1H, H-6a, J6a,6b 12.4 Hz,
J5,6a 4.6 Hz); 4.14 (dd, 1H, H-6b, J5,6b 2.1 Hz); 3.99 (m, 1H, H-5);

A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
17
2.06, 2.03, 2.01, 1.98 (s, 12H, 4x COCH3); 13C NMR (CDCl3,
125 MHz): d 191.2 (COCH3); 170.5, 169.9, 169.4, 169.3 (OCOCH3);
137.8 (Cqv.); 134.3 (Aryl-C), 128.3, 127.4 (Aryl-C); 79.7 (C-1); 77.3
(C-5); 73.9 (C-3); 69.9 (C-2); 68.0 (C-4); 61.7 (C-6); 22.6, 20.5,
20.5 (OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d 364. HRMS m/z
Calcd for: C21H24O10Se [M+Na]+: 539.042. Found: 539.043.
5.53 (d, 1H, H-1, J1,2 10.3 Hz); 5.45–5.30 (overlapping signals 2H,
H-2, H-3); 5.18 (t, 1H, H-3, J3,4 10.1 Hz); 4.31 (dd, 1H, H-6a, J6a,6b
12.4 Hz, J5,6a 4.6 Hz); 4.14 (dd, 1H, H-6b, J5,6b 2.1 Hz); 3.99 (m,
1H, H-5); 2.09, 2.06, 2.03, 2.00 (s, 12H, 4 ꢂ COCH3); 13C NMR
(CDCl3, 125 MHz): d 170.4, 169.8, 169.3, 169.2 (COCH3); 140.7
(Cqv.); 136.1 (Cqv.); 1291, 128.5 (Aryl-C); 79.8 (C-1); 77.2 (C-5);
73.7 (C-2); 69.7 (C-3); 67.8 (C-4); 61.6 (C-6); 20.5, 20.4, 20.3
(COCH3). 77Se NMR (CDCl3, 95 MHz): d 632. Anal. Calcd for
3.2.44. 1-Se-(4-Methylbenzoyl)-2,3,4,6-tetra-O-acetyl-b-D-
glucopyranose (45)30
C21H23ClO10Se: C, 45.87; H, 4.22. Found: C, 45.90; H, 4.33. HRMS
From 3 (55 mg, 0.10 mmol), p-toluoyl chloride (5p, 15 mg,
m/z Calcd for: C21H23ClO10Se [M+Na]+: 573.003. Found: 573.004.
0.20 mmol) and Et3N (27 lL, 0.11 mmol), 40 mg (74%), white solid,
mp 139–141 °C, lit.30 140–142, ½a D22
ꢀ
ꢁ6 (c 0.1, CHCl3), lit.30 ꢁ14 (c
3.2.48. 1,2:3,4-Di-O-isopropylidene-6-seleno-(2,3,4,6-tetra-O-
0.7, CHCl3); 1H NMR (CDCl3, 500 MHz): d 7.70 (dd, 2H, Aryl-H), 7.28
(dd, 2H, Aryl-H); 5.53 (d, 1H, H-1, J1,2 7.6 Hz); 5.37–5.32 (overlap-
ping signals 2H, H-2, H-3); 5.19 (t, 1H, H-4, J4,5 10.1 Hz); 4.31 (dd,
1H, H-6a, J6a,6b 12.7 Hz, J5,6a 4.2 Hz); 4.14 (dd, 1H, H-6b, J5,6b
2.0 Hz); 3.99 (m, 1H, H-5); 2.47 (s, 3H, CH3); 2.09, 2.06, 2.03, 2.00
(s, 12H, 4x COCH3); 13C NMR (CDCl3, 125 MHz): d 181.2 (CO),
161.7, 160.7, 160.0, 159.5 (OCOCH3); 145.2 (Cqv.); 135.0 (Cqv),
129.8, 126.3 (Aryl-C); 79.4 (C-1); 76.7 (C-5); 73.7 (C-3); 67.2 (C-
2); 61.4 (C-6); 21.4 (CH3); 20.3, 20.2, 201.1 (COCH3); 77Se NMR
(CDCl3, 95.4 MHz): d624, lit.30 622.8. Anal. Calcd for C22H26O10Se:
C, 49.91; H, 4.95. Found: C, 50.01; H, 4.79. HRMS m/z Calcd for:
acetyl-b-D-glucopyranosyl)-a-D
-galactopyranose (49)30
From 3 (110 mg, 0.20 mmol), 1,2:3,4-di-O-isopropylidene-6-O-
trifluromethanesulfonyl-galactopyranose30 (5s, 150 mg, 0.40
mmol) and Et3N (50
l
L, 0.40 mmol), 82 mg (62%), syrup, ½a D22
ꢀ
ꢁ46.8 (c 0.2, CHCl3), lit.30 ꢁ61 (c 1.3, CHCl3); 1H NMR (CDCl3,
500 MHz): d 5.50 (d, 1H, H-1Gal, J1,2 5.1 Hz); 5.20 (t, 1H, H-3Glc
,
J2,3 9.2 Hz); 5.08 (m, 2H, H-2Glc, H-4Glc); 4.88 (d, 1H, H-1Glc); 4.61
(dd, 1H, H-3Gal, J3,4 2.3 Hz); 4.34 (m, 1H, H-4Gal); 4.30 (dd, 1H, H-
2Gal); 4.23 (dd, 1H, H-6aGlc, J6a,6b 12.6 Hz, J5,6a 4.6 Hz); 4.12 (dd,
1H, H-6bGlc); 3.95 (t, 1H, H-5Gal); 3.67 (m, 1H, H-5Glc); 2.99 (dd,
1H, CH2aGal), 2.84 (dd, 1H, CH2bGal); 2.08, 2.04, 2.02, 1.98 (s, 12H,
4 ꢂ COCH3); 1.57, 1.41, 1.36, 1.32 (s, 12H, C(CH3)2); 13C NMR
(CDCl3, 125 MHz): d 170.8, 170.3, 169.6, 169.5 (COCH3); 109.5,
108.9 (Cqvacetal.); 96.7 (C-1Gal); 78.0 (C-1Glc); 77.2 (C-5Glc); 73.9
(C-3Glc); 72.1 (C-4Gal); 71.1 (C-3Gal); 70.6 (C-5Gal); 69.1 (C-2Gal);
68.5 (C-2,4Glc); 62.4 (C-6Glc); 26.2, 25.1; 24.7 (COCH3); 23.2 (C-
6Gal); 20.7, 20.6 (CH3)2; 77Se NMR (CDCl3, 95.4 MHz): d 280, lit.30
280.8. HRMS m/z Calcd for: C26H38O14Se [M+Na]+: 677.142. Found:
677.130.
C
22H26O10Se [M+Na]+: 553.069. Found: 553.063.
3.2.45. 1-Se-(4-Methylbenzoyl)-2-acetamido-2-deoxy-3,4,6-tri-
O-acetyl-b- -glucopyranose (46)
From 4 (100 mg, 0.10 mmol), p-toluoyl chloride (5p, 29 mg,
D
0.20 mmol) and Et3N (27 lL, 0.11 mmol), 75 mg (69%), white solid,
mp 175–177 °C, ½a D22
ꢀ
ꢁ7 (c 0.2, CHCl3); 1H NMR (CDCl3, 500 MHz):
d 7.71 (dd, 2H, Aryl-H), 7.26 (dd, 2H, Aryl-H); 5.94 (d, 1H, NH); 5.42
(d, 1H, H-1, J1,2 8.2 Hz); 5.22–5.17 (overlapping signals 2H, H-3, H-
4); 4.57 (t, 1H, H-2, J2,3 10.4 Hz); 4.28 (dd, 1H, H-6a, J6a,6b 12.4 Hz,
J5,6a 7.6 Hz); 4.13 (dd, 1H, H-6b, J5,6b 2.5 Hz); 3.87 (m, 1H, H-5);
2.41 (s, 3H, CH3); 2.08, 2.06 (s, 9H, 3 ꢂ COCH3); 1.88 (s, 3H, NHC-
OCH3); 13C NMR (CDCl3, 125 MHz): d 191.2 (CO), 171.0, 170.2,
169.8, 169.0 (COCH3); 145.2 (Cqv.); 135.2 (Cqv-CH3); 129.3, 127.2
(Aryl-C); 81.1 (C-1); 77.3 (C-5); 74.0 (C-3); 67.7 (C-4); 61.7 (C-6);
53.0 (C-2); 22.8 (CH3); 21.4, 20.4, 20.2 (COCH3); 77Se NMR (CDCl3,
95.4 MHz): d 364. Anal. Calcd for C22H27NO9Se: C, 50.01; H, 5.11; N,
2.65. Found: C, 49.84; H, 5.07; N, 2.69. HRMS m/z Calcd for:
3.2.49. 1,2:3,4-Di-O-isopropylidene-6-seleno-(2-acetamido-2-
deoxy-3,4,6-tri-O-acetyl-b-D-glucopyranosyl)-a-D-
galactopyranose (50)
From 4 (100 mg, 0.10 mmol), 1,2:3,4-di-O-isopropylidene-6-O-
trifluromethanesulfonyl-galactopyranose30 (5s, 150 mg, 0.40
mmol) and Et3N (50
l
L, 0.40 mmol), 76 mg (57%), syrup, ½a D22
ꢀ
ꢁ59 (c 0.1, CHCl3); 1H NMR (CDCl3, 500 MHz): d 6.02 (d, 1H,
NH); 5.47 (d, 1H, H-1Gal, J1,2 5.0 Hz); 5.12–4.98 (overplapping sig-
nals, 3H, H-4GlcNAc, H-3GlcNAc, H-1GlcNAc); 4.57 (dd, 1H, H-3Gal);
4.30–4.02 (overplapping signals, 4H, H-2Gal, H-4Gal, H-4GlcNAc, H-
6GlcNAc) 3.95 (m, 1H, H-5Gal); 3.62 (m, 1H, H-5GlcNAc); 2.97 (dd,
1H, CH2aGal), 2.75 (dd, 1H, CH2bGal); 2.04, 1.98, 1.90, 1.98 (s, 12H,
4 ꢂ COCH3); 1.48, 1.40, 1.30 (s, 12H, C(CH3)2); 13C NMR (CDCl3,
125 MHz): d 171.7, 171.6, 171.3, 169.9 (COCH3); 109.9, 109.3
(Cqvacetal); 97.7 (C-1Gal); 80.3 (C-1GlcNAc); 77.5 (C-5GlcNAc); 74.6
(C-4GlcNAc); 73.0 (C-4Gal); 71.5 (C-5Gal); 71.0 (C-2Gal); 70.2 (C-
3Gal); 69.2 (C-3GlcNAc); 63.9 (C-6GlcNAc); 54.5 (C-2GlcNAc); 23.2 (C-
6Gal); 26.7, 26.6, 25.5, 23.8 (OCOCH3); 21.6, 21.3 (CH3)2; 77Se
NMR (CDCl3, 95.4 MHz): d 292. HRMS m/z Calcd for: C26H37NO13Se
[M+Na]+: 676.147. Found: 676.148.
C
22H27NO9Se [M+Na]+: 552.074. Found: 552.075.
3.2.46. 1-Se-(4-Nitrobenzoyl)-2,3,4,6-tetra-O-acetyl-b-D-
glucopyranose (47)
From 3 (110 mg, 0.20 mmol), 4-nitrobenzoyl chloride (5q,
38 mg, 0.20 mmol) and Et3N (27 lL, 0.11 mmol), 80 mg (70%),
white solid, mp 152-154 °C, ½a D22
ꢀ
ꢁ14 (c 0.1, CHCl3); 1H NMR
(CDCl3, 500 MHz): d 8.35 (dd, 2H, Aryl-H), 8.03 (dd, 2H, Aryl-H);
5.58 (d, 1H, H-1, J1,2 10.9 Hz); 5.35–5.30 (overlapping signals 2H,
H-2, H-3); 5.19 (t, 1H, H-4, J3,4 9.7 Hz); 4.31 (dd, 1H, H-6a, J6a,6b
12.4 Hz, J5,6a 4.4 Hz); 4.15 (dd, 1H, H-6b, J5,6b 2.1 Hz); 3.92 (m,
1H, H-5); 2.09, 2.06, 2.04, 2.02 (s, 12H, 4 ꢂ COCH3); 13C NMR
(CDCl3, 125 MHz): d 190.4 (CO) 169.7, 169.4, 169.2 (COCH3);
149.3 (Cqv.); 142.5 (Cqv.); 128.3, 124.2 (Aryl-C); 80.2 (C-1); 77.2
(C-5); 73.8 (C-3); 69.8. (C-2); 67.9 (C-2); 61.6 (C-6); 20.6, 20.5
(COCH3); 77Se NMR (CDCl3, 95.4 MHz): d 364. Anal. Calcd for
3.2.50. Methyl-2,3-di-O-acetyl-4-seleno-(2-acetamido-2-deoxy-
3,4,6-tri-O-acetyl-b-
galactopyranoside (51)
From 4 (100 mg, 0.10 mmol), methyl 2,3,6-tri-O-benzyl-4-O-
trifluromethanesulfonyl- (5t, 236 mg,
-glucopyranoside1
0.40 mmol) and Et3N (56 L, 0.40 mmol), 110 mg (71%), syrup,
D-glucopyranosyl)-6-O-benzyl-a-D-
C
21H23NO12Se: C, 45.01; H, 4.14. Found: C, 45.60; H, 4.15. HRMS
a-D
l
m/z Calcd for: C21H23NO12Se [M+Na]+: 584.027. Found: 584.028.
½
a 2D2 +18 (c 0.2, CHCl3); 1H NMR (CDCl3, 500 MHz): d 7.40–7.34
ꢀ
3.2.47. 1-Se-(4-Chlorobenzoyl)-2,3,4,6-tetra-O-acetyl-b-
glucopyranose (48)
D
-
(m, 5H, Bn); 5.59 (d, 1H, NH); 5.38 (dd, 1H, H-3Gal, J3,4 4.0 Hz);
5.20 (d, 1H, H-1GlcNAc, J1,2 9.4 Hz); 5.18 (d, 1H, H-2Gal, J2,3 2.6 Hz);
From 3 (110 mg, 0.20 mmol), 4-chlorobenzoyl chloride (5r,
5.06 (dd, H-3GlcNAc); 5.04 (dd, 1H, H-4 GlcNAc); 4.95 (d, 1H, H-1Gal
,
35 mg, 0.20 mmol) and Et3N (27
l
L, 0.11 mmol), 75 mg (66%),
J1,2 3.8 Hz); 4.59 (dd, 2H, CH2Bn); 4.34 (m, 1H, H-5Gal); 4.14 (dd,
2H, H-6GlcNAc); 3.97 (dd, 1H, H-2GlcNAc); 3.85 (dd, 1H, H-4Gal);
3.78-3.67 (dd, 2H, H-6a,bGal); 3.57 (m, 1H, H-5GlcNAc); 2.95 (s, 3H,
white solid, mp 158-160 °C, ½a D22
ꢀ
ꢁ12 (c 0.2, CHCl3); 1H NMR
(CDCl3, 500 MHz): d 7.80 (dd, 2H, Aryl-H), 7.47 (dd, 2H, Aryl-H);

18
A. A. Kumar et al. / Carbohydrate Research 360 (2012) 8–18
OCH3); 2.13, 2.10, 2.06, 2.04, 1.97 (s, 18H, 6 ꢂ COCH3); 13C NMR
(CDCl3, 125 MHz): d 171.0, 170.6, 170.4, 170.3, 169.8, 169.3
(COCH3); 138.2 (Cqv.); 128.4, 127.7, 127.4 (Aryl-C); 97.1 (C-1Gal);
77.4 (C-5GlcNAc); 76.8 (C-4GlcNAc); 73.5 (C-1GlcNAc); 73.3 (CH2);
72.2 (C-6Gal); 70.6 (C-3Gal); 70.5 (C-2Gal); 69.1 (C-5Gal); 68.5 (C-3Glc-
NAc); 62.1 (C-6GlcNAc); 55.4 (OCH3); 43.89 (C-4Gal); 23.3 (NHCOCH3);
21.1, 20.9, 20.7, 20.6 (OCOCH3); 77Se NMR (CDCl3, 95.4 MHz): d
280. HRMS m/z Calcd for: C32H43NO15Se [M+Na]+: 784.169. Found:
784.169.
12. Mallet, A.; Mallet, J. M.; Sinaÿ, P. Tetrahedron: Asymmetry 1994, 5, 2593–2608.
13. Jiaang, W. T.; Chang, M. Y.; Tseng, P. H.; Chen, S. T. Tetrahedron Lett. 2000, 41,
3127–3130.
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appreciated.
We thank TÁMOP-4.2.1./B-09/1/KONV-2010-0007 for financial
support.
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