Aldol reaction of β-C-glycosylic ketones: synthesis of C-(E)-cinnamoyl glycosylic compounds as precursors for new biologically active C-glycosides

Article abstract of DOI:10.1016/j.carres.2008.04.021

A series of β-C-glycosylic ketones were prepared starting from d-glucose, d-xylose, d-mannose, and cellobiose. The β-C-glycosylic ketones on aldol condensation with different aromatic aldehydes in the presence of a suitable organocatalyst led to the forma

Full text of DOI:10.1016/j.carres.2008.04.021

Available online at www.sciencedirect.com
Carbohydrate Research 343 (2008) 1399–1406
Aldol reaction of b-C-glycosylic ketones: synthesis of
C-(E)-cinnamoyl glycosylic compounds as precursors
for new biologically active C-glycosidesI
Surendra Singh Bisht, Jyoti Pandey, Anindra Sharma and Rama Pati Tripathi*
Medicinal and Process Chemistry Division, Central Drug Research Institute, Lucknow 226 001, India
Received 17 March 2008; received in revised form 11 April 2008; accepted 16 April 2008
Available online 23 April 2008
Abstract—A series of b-C-glycosylic ketones were prepared starting from D-glucose, D-xylose, D-mannose, and cellobiose. The b-C-
glycosylic ketones on aldol condensation with different aromatic aldehydes in the presence of a suitable organocatalyst led to the
formation of respective C-(E)-cinnamoyl glycosides stereoselectively in good yields as precursors for the synthesis of biologically
active compounds.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords: Glycosylic ketones; Aldol reaction; C-Cinnamoyl glycosides
1. Introduction
tives A and B (Fig. 1) have recently been isolated as
natural products and are reported to possess plant
growth-inhibitory activity.23 Further, a,b-unsaturated
ketones serve as the core moiety in several natural
ligands for covalent bonding with many receptors.24
Encouraged with this report we were prompted to syn-
thesize such b-C-glycosylic ketones and determine their
scope in various other C–C bond forming reactions to
access a library of different C-glycosides. In the first
instance of its application, the aldol condensation of
b-C-glycosylic ketones were successfully carried out to
give respective C-cinnamoyl glycosides having the E
geometry at the double bond. The cinnamoyl glycosides
can be utilized in the synthesis of a library of organic
compounds by chemical manipulations of the double
bond25–27 and carbonyl group28 of the aglycon portion
The synthesis of C-glycosylic compounds (commonly
termed ‘C-glycosides’) has received considerable atten-
tion in recent years due to their occurrence in a variety
of natural products endowed with numerous biological
activities.1–7 The C-glycosides act as non-hydrolyzable
mimics of glycosyl amines (often termed N-glycosides)
and O-glycosides and are, therefore, useful in designing
new chemotherapeutics and biological tools.8–12 The
most common method for C–C bond formation at the
anomeric center involves nucleophilic attack on this nat-
urally electrophilic carbon atom.13–20 Very recently a few
reports have appeared where reactions of several D-gly-
coses with b-keto esters or ketones led to the formation
of b-C-glycosylic ketones in moderate to good yields.21,22
These glycosylic ketones may serve as intermediates
for the synthesis of several C-cinnamoyl glycosides.
The latter have great application in organic synthesis
and biochemistry as the 1-O-cinnamoyl glucose deriva-
O
HO
OH
O
O
O
HO
HO
HO
HO
O
O
OH
OH
O
O
q The term‘C-glycoside’ is commonly used for the correct terminology,
‘C-glycosylic compound’.
Corresponding author. Fax: +91 522 2623405/2623938/2629504;
e-mail: rpt.cdri@gmail.com
A
B
*
Figure 1. Plant growth-inhibitory 1-O-cinnamoyl glucose derivatives.
0008-6215/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2008.04.021

1400
S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
Table 1. Optimization of the aldol reaction of b-D-glucopyransoyl
ketone 1 with benzaldehyde at ambient temperature
and the hydroxyl functionalities of the sugar part. We
have carried out all the reactions under ambient condi-
tions with a view to find the most environment friendly
and economical method.
Entry Solvent
Catalyst
Reaction Yield (%)
(20 mol %) time (h)
1
2
3
4
5
MeOH
EtOH
n-BuOH
H2O
DMSO
CH2Cl2
Pyrrolidine 24
Pyrrolidine 24
Pyrrolidine 24
Pyrrolidine 24
Pyrrolidine 10
57
54
5
2. Results and discussion
No reaction
58
74
1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyranosyl)-, 1-(20,
30,40-tri-O-acetyl-b-D-xylopyranosyl)-, 1-(20,30,40,60-tetra-
O-acetyl-b-D-mannopyranosyl)-, and 1-(20,30,60,200,300,400,
6
Pyrrolidine
8
7
8
9
10
11
CH2Cl2 + H2O Pyrrolidine 24
5
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
DBU
8
8
8
8
No reaction
5
30
600-hepta-O-acetyl-b-cellobiosyl)-propan-2-ones
were
Piperidine
L-Proline
Et3N
prepared by the Knoevenagel condensation of 2,4-pen-
tanediones with D-glucose, D-xylose, D-mannose, and
cellobiose, respectively, followed by acetylation of the
hydroxyl groups present in the molecule following the
earlier protocol.29 The structures of all the b-C-glycosy-
lic ketones were in accord with their spectroscopic data
and microanalyses.22,29 Aldol condensation of the
above b-D-glucopyranosyl propanone (1) with different
aromatic aldehydes, viz. benzaldehyde, 3-nitro-, 4-meth-
oxy-, 3,4-dimethoxy-, 4-chlorobenzaldehydes, 2-naphth-
aldehyde, and pyridine-3-carboxaldehyde was carried
out separately at ambient temperature in the presence
of catalytic amount of pyrrolidine (20 mol %). To opti-
mize the reaction conditions, the condensation of
1-(20,30,40,60-tetra-O-acetyl-b-D-glucopyranosyl)-propan-
2-one (1) in different organic solvents and water under
the influence of various catalysts at ambient tempera-
ture was carried out to get the desired (E)-1-(20,30,40,60-
tetra-O-acetyl-b-D-glucopyranosyl)-4-phenylbut-3-en-2-
one (2) in varying yields (Scheme 1). Among the solvents
used, CH2Cl2 in the presence of pyrrolidine (20 mol %)
was found to be the most suitable combination to afford
the maximum yield (74%) of the desired compound 2.
Minor products (TLC) formed during the reaction could
not be isolated in pure form. The structure of (E)-1-
(20,30,40,60-tetra-O-acetyl-b-D-glucopyranosyl)-4-phenyl-
but-3-en-2-one (2) was established on the basis of its
NMR spectroscopic data and HRMS.
No reaction
products were established on the basis of their spectro-
scopic data and analyses.
To see the scope of this aldol condensation with other
sugars, the condensation of 1-(20,30,40-tri-O-acetyl-b-D-
xylopyranosyl)-propan-2-one (9) with benzaldehyde,
3-nitrobenzaldehyde,
and
4-methoxybenzaldehyde
separately led to the formation of respective (E)-1-
(20,30,40-tri-O-acetyl-b-D-xylopyranosyl)-4-phenylbut-3-
en-2-ones (10–12) in good yields (Table 2, entries 8–10).
However, the aldol reaction of 1-(20,30,40,60-tetra-O-acet-
yl-b-D-mannopyranosyl)-propan-2-one (13) was carried
out only with 3-nitrobenzaldehyde to give the respective
(E)-1-(20,30,40,60-tetra-O-acetyl-b-D-mannopyranosyl)-4-
(3-nitrophenyl)but-3-en-2-one (14) in 70% yield (Table
2, entry 11). The structures of compounds 10–12 and
14 were in accord with their spectroscopic data and
microanalyses.
Finally, the aldol condensation of a disaccharide-
derived b-glycosylic ketone, 1-(20,30,60,200,300,400,600-hepta-
O-acetyl-b-cellobiosyl)propan-2-one (15) with benzalde-
hyde, 3,4-dimethoxybenzaldehyde, and naphthaldehyde
under the above experimental conditions led to the for-
mation of respective (E)-1-(20,30,60,200,300,400,600-hepta-O-
acetyl-b-cellobiosyl)-4-phenylbut-3-en-2-ones (16–18) in
good yields (Table 2, entries 12–14).
Similarly, condensation of the above b-D-glucosyl
ketone 1 with different aldehydes, viz. 3-nitro-, 4-meth-
oxy-, 3,4-dimethoxy-, 4-chlorobenzaldehydes, 2-naph-
thaldehyde, and pyridine-3-carboxaldehyde under the
above optimum reaction conditions (Table 1 entry 6)
led to the formation of respective 1-(20,30,40,60-tetra-O-
acetyl-b-D-glucopyranosyl)-propan-2-ones (3–8) in good
yields (Table 2, entries 1–7). The structures of all the
3. Conclusions
We have prepared b-C-glycosylic ketones of D-glucose,
D-xylose, D-mannose, and D-cellobiose. The b-C-gly-
cosylic ketones on aldol reaction with different alde-
hydes under ambient reaction conditions resulted in
OAc
OAc
CHO
O
O
Catalyst
Solvent
AcO
AcO
AcO
+
AcO
OAc
OAc
O
O
1
2
Scheme 1. Aldol reaction of b-C-glycosylic ketone 1 in the presence of various solvents.

S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
1401
Table 2. Synthesis of C-glycosylic phenylbutenones by reaction of glycosylic ketones 1, 9, 13 and 15 with different aldehydes
Entry
Substrate
Reaction
time (h)
Product
% Yield
Glycosylic
ketone
Aldehyde
CHO
OAc
1
8
74
O
AcO
AcO
OAc
O
O
2
CHO
OAc
OAc
NO2
O
2
3
7
9
70
69
AcO
AcO
NO2
OAc
3
4
OCH3
CHO
OAc
O
AcO
AcO
O
AcO
AcO
OAc
O
OAc
OCH3
CHO
1
O
O
O
OCH3
OCH3
OAc
OAc
O
4
5
10
73
66
AcO
AcO
OCH3
OAc
OCH3
CHO
5
6
Cl
O
9
AcO
AcO
OAc
Cl
OAc
OAc
CHO
O
AcO
AcO
6
7
11
10
73
71
OAc
O
O
O
7
8
N
CHO
N
O
AcO
AcO
OAc
CHO
CHO
O
AcO
AcO
8
9
9
8
70
70
OAc
10
O
AcO
AcO
NO2
O
OAc
AcO
AcO
O
OAc
9
NO2
O
O
11
OCH3
CHO
O
10
11
9
8
75
AcO
AcO
OAc
OCH3
CHO
12
OAc
OAc
OAc
OAc
O
NO2
O
70
AcO
AcO
AcO
AcO
13
NO2
O
14 O
(continued on next page)

1402
S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
Table 2 (continued)
Entry
Substrate
Reaction Product
time (h)
% Yield
Glycosylic
ketone
Aldehyde
CHO
OAc
OAc
12
10
71
O
O
AcO
AcO
O
AcO
OAc
OAc
O
16
OCH3
OCH3
CHO
OAc
OAc
OAc
OAc
OAc
O
O
AcO
AcO
O
13
11
70
67
O
O
AcO
O
AcO
AcO
OCH3
OAc
AcO
OAc
OAc
OAc
O
OCH3
O
15
17
OAc
CHO
O
O
AcO
AcO
14
9
O
AcO
OAc
OAc
O
18
the respective (E)-1-(glycopyranosyl)-4-phenylbut-3-en-
2-ones stereoselectively in good yields. The synthesized
C-cinnamoyl glycoside congeners are being used as pre-
cursors for the synthesis of a library of potentially bio-
logically active compounds.
1.03 mmol) and benzaldehyde (0.60 mL, 5.66 mmol).
After stirring at room temperature for given the time,
the reaction mixture was evaporated under reduced
pressure and extracted by EtOAc–water. The EtOAc
layer was dried by Na2SO4 and concentrated. The prod-
uct was purified by column chromatography on silica gel
(60–120 mesh) using 4:6 EtOAc–hexane as eluent to give
compound 1 as a colorless solid: mp 101–102 °C; yield
4. Experimental
25
1.8 g (74%); Rf 0.5 (6:4 hexane–EtOAc); ½aꢁD ꢀ18 (c
4.1. General methods
0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2925, 1747, 1652;
1H NMR (300 MHz, CDCl3 + CCl4): d 7.57–7.52 (m,
3H, ArH, H-4), 7.41–7.39 (m, 3H, Ar-H), 6.70 (d, 1H,
J 16.2 Hz, H-3), 5.22 (t, 1H, J 9.3 Hz, H-40), 5.06 (t,
1H, J 9.5 Hz, H-20), 4.98 (t, 1H, J 9.5 Hz, H-30), 4.26
Commercially available reagent grade chemicals were
used as received. All reactions were followed by TLC
on E. Merck Kieselgel 60 F254, with detection by UV
light, spraying 20% aq KMnO4 solution and/or spraying
4% ethanolic H2SO4. Column chromatography was per-
formed on Silica Gel (60–120 mesh and 100–200 mesh,
E. Merck). IR spectra were recorded as thin films or in
KBr solution with a Perkin–Elmer Spectrum RX-1
(dd, 1H, J5 ;6 b 4.8 Hz, J6 a;6 b 12.3 Hz, H-60b), 4.12
0
0
0
0
0
0
0
0
(ddd, 1H, J1 ;2 11.5 Hz, J1 ;1a 8.4 Hz, J1b;1 3.3 Hz, H-
10), 4.00 (dd, 1H, J6 a;5 1.9 Hz, J6 b;6 a 12.3 Hz, H-60a),
0
0
0
0
0
0
0
0
0
0
3.71 (ddd, 1H, J4 ;5 9.9 Hz, J5 ;6 a 4.7 Hz, J5 ;6 b 2.1 Hz,
H-50), 3.00 (dd, 1H, J1 ;1b 8.3 Hz, J1a,1b 16.2 Hz, H-1b),
1
(4000–450 cmꢀ1) spectrophotometer. H and 13C NMR
0
2.70 (dd, 1H, J1b,1 3.2 Hz J1a,1b 16.2 Hz, H-1a) 2.03,
2.02, 2.01, 1.98 (s, 12H, –OCOCH3). 13C NMR
(50 MHz, CDCl3): d 196.0 (C@O), 170.6, 170.3, 170.1,
169.6, (4 ꢂ –OCOCH3), 145.2 (Ar-C), 143.9 (C-4),
131.0 (C-3), 129.7, 129.6, 129.3, 129.0, 128.7, (ArCH),
75.2 (C-50), 74.5 (C-10), 72.2 (C-30), 70.3 (C-20), 68.9
(C-40), 62.3 (C-60), 43.1 (C-1), 21.04 and 20.9 (4 ꢂ
–OCOCH3); ESIMS: m/z 477 (M+H)+; HRMS m/z:
calcd for C24H28O10, 476.1682; found, 476.1678.
spectra were recorded on Bruker DRX 300-MHz and
75-MHz instruments, respectively, in CDCl3. Chemical
shift values are reported in ppm relative to TMS (tetra-
methylsilane) as the internal reference, unless otherwise
stated; s (singlet), d (doublet), t (triplet), m (multiplet);
J in Hertz. FAB mass spectra were performed using a
Jeol SX-102 mass spectrometer and ESI mass spectra
were performed using a Quattro II (Micromass) instru-
ment. Optical rotations were measured in a 1.0-dm tube
with a Rudolf Autopol III polarimeter in CHCl3. Excess
of solvent was evaporated under reduced pressure at a
bath temperature of 55 and 60 °C.
4.2.1.
(E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyran-
osyl)-4-(3-nitrophenyl)-but-3-en-2-one (3). Compound
3 was obtained by the reaction of b-glycosylic ketone 1
(1.5 g, 3.86 mmol) and 3-nitrobenzaldehyde (0.64 g,
3.91 mmol) as a colorless solid: mp 71–72 °C; yield
4.2. General procedure for (E)-1-(20,30,40,60-tetra-O-
acetyl-b-D-glucopyranosyl)-4-phenylbut-3-en-2-one (2)
25
1.4 g (70%); Rf 0.4 (7:3 hexane–EtOAc); ½aꢁD ꢀ30 (c
To a solution of b-glycosylic ketone 1 (2.0 g, 5.15 mmol)
in dry CH2Cl2 were added pyrrolidine (0.085 mL,
0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2926, 1751, 1666;
1H NMR (300 MHz, CDCl3 + CCl4): d 8.41 (s,1H, Ar-

S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
1403
0
0
H), 8.24 (d, 1H, J 7.7 Hz, Ar-H), 7.84 (d, 1H, J 7.7 Hz,
Ar-H), 7.62–7.54 (m, 2H, Ar-H, H-4), 6.85 (d, 1H, J
16.2 Hz H-3) 5.20 (t, 1H, J 9.3 Hz, H-40), 5.05 (t, 1H,
J 9.7 Hz, H-20), 4.95 (t, 1H, J 9.5 Hz, H-30), 4.25 (dd,
4.7 Hz, J6 a;6 b 12.4 Hz, H-60b), 4.01 (ddd, 1H, J1a,1
8.3 Hz, J1b,1 3.2 Hz, H-10), 3.98 (dd, 1H, J6 a;5 1.7 Hz,
0
0
H-60a), 3.87 (s, 6H, –OCH3X2), 3.66 (ddd, 1H, J5 ;4
0
0
9.7 Hz, J5 ;6 a 4.4 Hz, J5 ;6 b 1.9 Hz, H-50), 2.95 (dd, 1H,
0
0
0
0
1H, J5 ;6 b 4.7 Hz, J6 a;6 b 12.4 Hz, H-60b), 4.09 (ddd,
J1b,1 8.3 Hz, J1a,1b 16.1 Hz, H-1b), 2.58 (dd, 1H, J1a;1
0
0
0
0
0
1H, J1 ;2 11.6 Hz, J1a;1 8.8 Hz, J1b;1 3.0 Hz, H-10), 4.00
3.1 Hz J1a,1b 16.2 Hz, H-1a), 2.04–2.00 (4s, 12H, 4 ꢂ
–OCOCH3). 13C NMR (50 MHz, CDCl3): d 196.1 (C@O,
C-2), 171.8 and 170.2 (4 ꢂ –OCOCH3), 152.1, 149.8,
143.8, 127.8, 124.8, 123.6, 111.8, 110.1, 75.8 (C-50), 75.6
(C-10), 74.9 (C-30), 72.1 (C-20), 68.8 (C-40), 62.2 (C-60),
56.2 (OCH3), 56.1 (OCH3) 42.8 (C-1), 21.04 and 20.9
(4 ꢂ –OCOCH3); ESIMS: m/z 559 (M+Na)+, HRMS
m/z: calcd for C26H32O12, 5.1894; found, 536.1891.
0
0
0
0
(dd, 1H, J6 a;5 1.8 Hz, J6 b;6 a 12.3 Hz, H-60a), 3.70
0
0
0
0
0
0
0
0
0
0
(ddd, 1H, J4 ;5 9.9 Hz, J5 ;6 a 4.5 Hz, J5 ;6 b 2.1 Hz, H-
50), 3.02 (dd, 1H, J1b;1 8.4 Hz, J1a,1b 16.3 Hz, H-1b),
0
0
2.68 (dd, 1H, J1a;1 3.1 Hz J1a,1b 16.3 Hz, H-1a), 2.02–
1.98 (4s, 12H, 4 ꢂ –OCOCH3). 13C NMR (50 MHz,
CDCl3): d 193.0 (C@O, C-2), 168.8 and 167.9, (4 ꢂ
–OCOCH3), 147.5, 139, 134, 132, 128, 127, 123, 121,
75.8 (C-50), 74.6 (C-10), 72.7 (C-30), 70.3 (C-20), 67 (C-
40), 60 (C-60), 41.8 (C-1), 21.02 and 20.9 (4 ꢂ
–OCOCH3); ESIMS: m/z 544 (M+Na)+; HRMS m/z:
calcd for C24H27NO12, 521.1533; found, 521.1550.
4.2.4.
(E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyran-
osyl)-4-(4-chlorophenyl)but-3-en-2-one (6). Compound
6 was obtained by the reaction of b-glycosylic ketone 1
(1.5 g, 3.86 mmol) and 4-chlorobenzaldehyde (0.54 g,
3.86 mmol) as a colorless solid: mp 151–152 °C; yield
4.2.2. (E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyrano-
25
syl)-4-(4-methoxyphenyl)but-3-en-2-one
(4). Com-
1.3 g (66%); Rf 0.5 (7:3 hexane–EtOAc); ½aꢁD ꢀ18 (c
pound 4 was obtained by the reaction of b-glycosylic
ketone 1 (2.0 g, 5.15 mmol) and 4-methoxybenzaldehyde
(0.958 g, 5.15 mmol) as a colorless solid: mp 158–160 °C;
0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2943, 2877, 1748,
1
1598; H NMR (300 MHz, CDCl3 + CCl4): d 7.50–7.42
(m, 3H, Ar-H, H-4), 7.34 (d, 2H, J 8.5 Hz, Ar-H), 6.66
(d, 1H, J 16.2 Hz, H-3), 5.18 (t, 1H, J 9.2 Hz, H-40),
5.02 (t, 1H, J 9.6 Hz, H-20), 4.92 (t, 1H, J 9.4 Hz, H-
30), 4.27 (dd, 1H, J5 ;6 b 4.7 Hz, J6 a;6 b 12.4 Hz, H-60b),
25
yield 1.8 g (69%); Rf 0.4 (7:3 hexane–EtOAc); ½aꢁD ꢀ39
(c 0.1, CHCl3); IR (KBr) mmax cmꢀ1: 3022, 2953, 1748,
1598; 1H NMR (300 MHz, CDCl3 + CCl4): d 7.52–
7.47 (m, 3H, Ar-H, H-4), 6.89 (d, 2H, J 8.6 Hz, Ar-H),
6.59 (d, 1H, J 16.2 Hz, H-3), 5.19 (t, 1H, J 9.3 Hz, H-
40), 5.06 (t, 1H, J 9.6 Hz, H-20), 4.96 (t, 1H, J 9.5 Hz,
0
0
0
0
0
0
0
0
4.06 (ddd, 1H, J1 ;2 11.5 Hz, J1b;1 3.2 Hz, J1a;1 8.5 Hz,
H-10), 3.97 (dd, 1H, J6 a;5 1.9 Hz, J6 b;6 a 12.4 Hz, H-
0
0
0
0
60a), 3.67 (ddd, 1H, J5 ;4 9.7 Hz, J5 ;6 a 4.3 Hz, J5 ;6 b
0
0
0
0
0
0
H-30), 4.25 (dd, 1H, J5 ;6 b 4.8 Hz, J6 a;6 b 12.4 Hz, H-
2.0 Hz, H-50), 2.97 (dd, 1H, J1b;1 8.4 Hz, J1a,1b 16.3 Hz,
0
0
0
0
0
60b), 4.10 (ddd, 1H, J1 ;2 11.4 Hz, J1b,1 3.1 Hz, H-10),
H-1b), 2.63 (dd, 1H, J1a;1 3.1 Hz J1a,1b 16.3 Hz, H-1a)
0
0
0
4.00 (dd, 1H, J6 a;5 1.3 Hz, J6 b;6 a 12.3 Hz, H-60a), 3.83
2.00–1.70 (4s, 12H, –OCOCH3). 13C NMR (50 MHz,
CDCl3): d 195.8 (C@O, C-2), 170.5, 170.2, 170.0, 169.6,
(4 ꢂ –OCOCH3), 142.3, 137.1, 133.1, 129.8, 129.7,
127.0, 76.2 (C-50), 74.54 (C-10), 74.51 (C-30), 72.0 (C-20),
68.8 (C-40), 62.3 (C-60), 43.2 (C-1), 21.03 and 20.94
(4 ꢂ –OCOCH3); ESIMS: m/z 533 (M+Na)+, HRMS
m/z: calcd for C24H27ClO10, 510.1292; found, 510.1291.
0
0
0
0
0
0
0
0
(s, 3H, –OCH3) 3.70 (ddd, 1H, J5 ;6 a 4.5 Hz, J5 ;6 b
2.7 Hz, H-50), 2.99 (dd, 1H, J1b;1 8.3 Hz, J1a,1b
0
0
16.1 Hz, H-1b), 2.64 (dd, 1H, J1a;1 3.1 Hz J1a,1b
16.2 Hz, H-1a) 2.04–2.00 (4s, 12H, 4 ꢂ –OCOCH3).
13C NMR (50 MHz, CDCl3): d 196.1 (C@O, C-2),
170.7, 170.4, 170.1, 169.7, (4 ꢂ –OCOCH3), 143.8,
130.5, 127.2, 124.4, 114.8, 76.1 (C-50), 74.6 (C-10), 72.1
(C-30), 70.5 (C-20), 68.8 (C-40), 62.3 (C-60), 55.6
(OCH3), 42.8 (C-1), 21.05 and 20.9 (4 ꢂ –OCOCH3);
ESIMS: m/z 529 (M+Na)+, HRMS m/z: calcd for
C25H30O11, 506.1789; found, 506.1786.
4.2.5.
osyl)-4-(2-napthyl)but-3-en-2-one (7). Compound
(E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyran-
7
was obtained by the reaction of b-glycosylic ketone 1
(2.0 g, 5.91 mmol) and 2-napthaldehyde (0.93 g,
3.86 mmol) as a colorless solid: mp 158–160 °C; yield
25
4.2.3.
(E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyran-
2.0 g (73%); Rf 0.4 (6:4 hexane–EtOAc); ½aꢁD ꢀ34 (c
osyl)-4-(3,4-dimethoxyphenyl)but-3-en-2-one (5). Com-
pound 5 was obtained by the reaction of b-glycosylic
ketone 1 (1.5 g, 3.86 mmol) and 3,4-dimethoxybenzlde-
hyde (0.64 g, 3.86 mmol) as a colorless solid: mp 147–
148 °C; yield 1.3 g (73%); Rf 0.3 (5:5 hexane–EtOAc);
0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2954, 1744, 1653;
1H NMR (300 MHz, CDCl3 + CCl4): d 7.94 (s,1H, Ar-
H), 7.83–7.79 (m, 3H, Ar-H, H-4), 7.66–7.63 (m, 2H,
Ar-H), 7.52–7.47 (m, 2H, Ar-H) 5.16 (t, 1H, J 9.2 Hz,
H-40), 5.02 (t, 1H, J 9.6 Hz, H-20), 4.97 (t, 1H, J
25
½aꢁD ꢀ25 (c 0.1, CHCl3); IR (KBr) mmax cmꢀ1: 3020,
9.5 Hz, H-30), 4.26 (dd, 1H, J5 ;6 b 4.7 Hz, J6 a;6 b
0
0
0
0
1
0
0
0
2945, 1747, 1652; H NMR (300 MHz, CDCl3 + CCl4):
12.4 Hz, H-60b), 4.10 (ddd, 1H, J1 ;2 11.5 Hz, J1b;1
0
0
0
d 7.40 (d, 1H, J 16.1 Hz, H-4), 7.10–7.01 (m, 2H, Ar-H),
6.81 (d, 2H, J 8.3 Hz, Ar-H), 6.54 (d, 1H, J 16.1 Hz, H-
3), 5.15 (t, 1H, J 9.3 Hz, H-40), 4.99 (t, 1H, J 9.6 Hz, H-
3.2 Hz, H-10), 4.00 (dd, 1H, J6 b;50 1.8 Hz, J6 b;6 a
12.3 Hz, H-60a), 3.70 (ddd, 1H, J4 ;5 9.3 Hz, J5 ;6 a
0
0
0
0
4.5 Hz, J5 ;6 b 2.1 Hz, H-50), 3.02 (dd, 1H, J1b;1 8.3 Hz,
J1a,1b 16.3 Hz, H-1b), 2.64 (dd, 1H, J1a,1 3.1 Hz J1a,1b
0
0
0
20), 4.91 (t, 1H, J 9.4 Hz, H-30), 4.23 (dd, 1H, J5 ;6 b
0
0

1404
S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
16.2 Hz, H-1a), 2.01–1.99 (4s, 12H, 4 ꢂ –OCOCH3). 13
C
(C-1), 31.1 and 20.9 (3 ꢂ –OCOCH3); ESIMS: m/z 427
(M+Na)+, HRMS m/z: calcd for C22H26O9, 404.1515;
found, 404.1471.
NMR (50 MHz, CDCl3): d 196.0 (C@O, C-2), 169.6 and
170.6, (4 ꢂ –OCOCH3), 144.0, 134.8, 133.7, 132.1,
131.1, 129.2, 129.0, 128.2, 127.8, 127.2, 126.7, 123.8,
76.7 (C-50), 76.2 (C-10), 74.6 (C-30), 72.1 (C-20), 68.8
(C-40), 62.3 (C-60), 43.1 (C-1), 21.0 and 20.9 (4 ꢂ
–OCOCH3); ESIMS: m/z 449 (M+Na)+, HRMS m/z:
calcd for C28H30O10, 526.1839; found, 526.1845.
4.3.1. (E)-1-(20,30,40-Tri-O-acetyl-b-D-xylopyranosyl)-4-
(3-nitrophenyl)but-3-en-2-one (11). Compound 11 was
obtained by the reaction of b-glycosylic ketone 9
(0.5 g, 1.58 mmol) and 3-nitrobenaldehyde (0.238 g,
1.58 mmol) as a colorless solid: mp 110–114 °C; yield
25
4.2.6.
(E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-glucopyran-
0.53 g (75%); Rf 0.4 (7:3 hexane–EtOAc); ½aꢁD ꢀ40 (c
osyl)-4-(3-pyridyl)but-3-en-2-one (8). Compound 8 was
obtained by the reaction of b-glycosylic ketone 1 (1.5 g,
3.86 mmol) and pyridine-3-carboxyaledehyde (0.36 mL,
3.86 mmol) as a colorless solid: mp 140–141 °C; yield
0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2920, 2361, 1747,
1
1532; H NMR (300 MHz, CDCl3 + CCl4): d 8.40 (s,
1H, Ar-H), 8.24 (d, 1H, J 5.4 Hz, Ar-H), 7.84 (d, 1H,
J 5.1 Hz, Ar-H), 7.62–7.55 (m, 2H, Ar-H, H-3), 6.87
(d, 1H, J 10.7 Hz, H-4), 5.19 (t, 1H, J 9.3 Hz, H-50b),
4.97–4.92 (m, 2H, H-10), 4.89 (t, 1H, J 9.5 Hz, H-50a),
4.07–4.01 (m, 2H, H-30, H-40), 3.31 (t, 1H, J 10.8 Hz,
25
1.27 g (71%); Rf 0.3 (5:5 hexane–EtOAc); ½aꢁD ꢀ26 (c
0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2941, 2880, 1747,
1691, 1616; 1H NMR (300 MHz, CDCl3 + CCl4): d 8.75
(s, 1H, Ar-H), 8.60 (d, 1H, J 3.6 Hz, Ar-H), 7.84 (d, 1H,
J 7.9 Hz, Ar-H), 7.52 (d, 1H, J 16.3 Hz, H-4), 7.35–7.30
(m, 1H, Ar-H), 6.76 (d, 1H, J 16.3 Hz, H-3), 5.19 (t, 1H,
J 9.3 Hz, H-40), 5.04 (t, 1H, J 9.8 Hz, H-20), 4.942 (t,
H-20), 3.02 (dd, 1H, J1b;1 8.7 Hz, J1a,1b 16.3 Hz, H-1b),
0
0
2.69 (dd, 1H, J1a;1 2.97 Hz, J1a,1b 16.1 Hz, H-1a),
2.03–2.02 (ts, 9H, 3 ꢂ –OCOCH3). 13C NMR
(50 MHz, CDCl3): d 195.8 (C@O), 170.2, 170.0, 169.8
(3 ꢂ –OCOCH3), 149.2, 140.7, (Ar-C and C-4), 136.5
(C-3), 134.1, 130.3, 129.0, 125.1, 123.0 (ArCH), 75.1
(C-50), 74.0 (C-10), 72.2 (C-30), 69.5 (C-20), 67.1 (C-40),
43.4 (C-1), 31.2 and 21.0 (3 ꢂ –OCOCH3); ESIMS:
m/z 472 (M+Na)+; HRMS m/z: calcd for C21H23-
NO10, 449.1321; found, 449.1312.
1H, J 9.7 Hz, H-30), 4.23 (dd, 1H, J5 ;6 b 4.8 Hz, J6 a;6 b
0
0
0
0
12.4 Hz, H-60b), 4.09 (ddd, 1H, J1 ;2 11.5 Hz, J1b;1
0
0
0
3.1 Hz, J1a;1 8.8 Hz, H-10), 3.98 (dd, 1H, J6 a;5 1.7 Hz,
0
0
0
J6 b;6 a 12.4 Hz, H-60a), 3.69 (ddd, 1H, J5 ;4 9.9 Hz, J5 ;6 a
0
0
0
0
0
0
4.5 Hz, J5 ;6 b 2.0 Hz, H-50), 3.00 (dd, 1H, J1b;1 8.5 Hz,
0
0
0
0
J1a,1b 16.3 Hz, H-1b), 2.63 (dd, 1H, J1a;1 3.1 Hz J1a,1b
16.3 Hz, H-1a) 2.03, 2.01, 1.996, 1.990 (4s, 12H, 4 ꢂ
–OCOCH3). 13C NMR (50 MHz, CDCl3): d 195.3
(C@O, C-2), 170.2, 169.9, 169.7, 169.2, (4 ꢂ –OCOCH3),
151.3, 150.0, 139.6, 134.2, 130.0, 127.8, 123.7, 75.8 (C-50),
74.08 (C-10), 74.03 (C-30), 71.6 (C-20), 68.3 (C-40), 61.8 (C-
60), 42.8 (C-1), 20.63 and 20.53 (4 ꢂ –OCOCH3); ESIMS:
m/z 500 (M+Na)+, HRMS m/z: calcd for C23H27NO10,
477.1634; found, 477.1640.
4.3.2. (E)-1-(20,30,40-Tri-O-acetyl-b-D-xylopyranosyl)-4-
(4-methoxyphenyl)but-3-en-2-one (12). Compound 12
was obtained by the reaction of b-glycosylic ketone
9
(0.5 g, 1.58 mmol) and 4-methoxybenzaldehyde
(0.21 mL, 1.58 mmol) as a colorless solid: mp 140–
145 °C; yield 0.48 g (70%); Rf 0.4 (7:3 hexane–EtOAc);
25
½aꢁD ꢀ52 (c 0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2928,
1
2361, 1739, 1530; H NMR (300 MHz, CDCl3 + CCl4):
4.3. (E)-1-(20,30,40-Tri-O-b-D-xylopyranosyl)-4-phenylbut-
3-en-2-one (10)
d 7.51–7.48 (m, 3H, Ar-H and H-3), 6.92 (d, 2H, J
8.73 Hz, Ar-H), 6.64 (d, 1H, J 16.1 Hz, H-4), 5.19 (t,
1H, J 9.3 Hz, H-50b), 4.99–4.94 (m, 2H, H-1), 4.91 (t,
1H, J 9.5 Hz, H-50a), 4.07–4.02 (m, 2H, H-30, H-40),
3.85 (s, 1H, –OCH3), 3.32 (t, 1H, J 10.8 Hz, H-20),
Compound 10 was obtained by the reaction of b-gly-
cosylic ketone 9 (0.5 g, 1.58 mmol) and benzaldehyde
(0.163 mL, 1.58 mmol) as a colorless solid: mp 112–
116 °C; yield 0.45 g (70%); Rf 0.4 (7:3 hexane–EtOAc);
0
2.98 (dd, 1H, J1b;1 8.5 Hz, J1a,1b 15.9 Hz, H-1a), 2.63
0
(dd, 1H, J1a;1 3.1 Hz, J1a,1b 15.9 Hz, H-1a), 2.03–2.02
25
½aꢁD ꢀ62 (c 0.1, CHCl3); IR (KBr) mmax cmꢀ1: 3021,
(ts, 9H, 3 ꢂ –OCOCH3). 13C NMR (50 MHz, CDCl3):
d 196.0 (C@O), 170.2, 170.0, 169.7 (3 ꢂ –OCOCH3),
162.1, 143.7, (Ar-C and C-4), 127.3 (C-3), 130.5, 124.5,
114.8 (ArCH), 75.3 (C-50), 74.2 (C-10), 72.4 (C-30), 69.7
(C-20), 67.1 (C-40), 55.6 (OCH3), 42.9 (C-1), 21.0 (3 ꢂ
–OCOCH3); ESIMS: m/z 457 (M+Na)+, HRMS m/z:
calcd for C22H26O9, 434.1577; found, 434.1543.
1
2361, 1747, 1600; H NMR (300 MHz, CDCl3 + CCl4):
d 7.54–7.38 (m, 3H, Ar-H and H-3), 7.38–7.27 (m, 3H,
Ar-H), 6.73 (d, 1H, J 16.2 Hz, H-4), 5.19 (t, 1H, J
9.3 Hz, H-50b), 4.99–4.90 (m, 1H, H-10), 4.87 (t, 1H, J
9.6 Hz, H-50a), 4.05–3.96 (m, 2H, H-30, H-40), 3.34 (t,
1H, J 10.8 Hz, H-20), 2.98 (dd, 1H, J1b;1 8.5 Hz, J1a,1b
0
0
16.0 Hz, H-1b), 2.62 (dd, 1H, J1a;1 3.1 Hz, J1a,1b
16.0 Hz, H-1a), 2.02–2.01 (ts, 9H, 3 ꢂ –OCOCH3). 13C
NMR (50 MHz, CDCl3): d 195.8 (C@O), 169.9, 169.8,
169.5 (3 ꢂ –OCOCH3), 143.7 (Ar-C and C-4), 134.7
(C-3), 130.9, 129.3, 128.7, 126.7 (ArCH), 75.2 (C-50),
74.1 (C-10), 72.3 (C-30), 69.6 (C-20), 67.1 (C-40), 43.0
4.4. (E)-1-(20,30,40,60-Tetra-O-acetyl-b-D-mannopyran-
osyl)-4-(3-nitrophenyl)but-3-en-2-one (14)
Compound 14 was obtained by the reaction of b-gly-
cosylic ketone 13 (1.5 g, 3.86 mmol) and 3-nitrobenalde-

S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
1405
hyde (0.64 g, 3.91 mmol), as a colorless solid: mp 130–
Ar-H), 7.05 (s, 1H, Ar-H), 6.83 (d, 1H, J 8.2 Hz,
Ar-H), 6.57 (d, 1H, J 16.0 Hz, H-3), 5.15 (t, 1H, J
9.2 Hz, H-30), 5.08–5.00 (m, 2H, H-300, H-400), 4.90–4.79
(m, 2H, H-20, H-200), 4.51 (d, 1H, J 8.4 Hz, H-100), 4.39–
4.33 (m, 2H, H-60b, H-60a), 4.14–3.98 (m, 3H, H-600b,
H-600a, H-10), 3.91 (s, 6H, 2 ꢂ –OCH3), 3.73–3.62
132 °C; yield 1.4 g (70%); Rf 0.4 (1:1 hexane–EtOAc);
25
½aꢁD ꢀ28 (c 0.1, CHCl3); IR (KBr) mmax cmꢀ1 2926,
1742, 1636; 1H NMR (300 MHz, CDCl3 + CCl4): d
8.40 (s,1H, Ar-H), 8.23 (d, 1H, J 7.7 Hz, Ar-H), 7.85
(d, 1H, J 7.7 Hz, Ar-H), 7.62–7.54 (m, 2H, Ar-H, H-
4), 6.83 (d, 1H, J 16.2 Hz H-3), 5.35 (d, 1H, J 3.0 Hz,
H-40), 5.21–5.10 (m, 2H, H-20, H-30), 4.32–4.24 (m, 2H,
H-10, H-60b), 4.03 (d, J 12.3 Hz, H-60a), 3.70 (ddd, 1H,
(m, 3H, H-500, H-50, H-40), 2.86 (dd, 1H, J1b;1 8.4 Hz,
0
0
J1a,1b 16.0 Hz, H-1b), 2.62 (dd, 1H, J1a;1 3.1 Hz
J1a,2b 16.0 Hz, H-1a), 2.10–2.00 (7s, 21H, 7 ꢂ
–OCOCH3). 13C NMR (50 MHz, CDCl3): d 194.9
(C@O, C-2), 169.8 and 168.4, (7 ꢂ –OCOCH3), 151.5,
149.3, 143.2 (C-4), 127.2, 124.1, 123.1, 111.0, 109.8,
100.7 (C-100), 76.7, 76.6, 74.1, 73.8, 73.6, 72.9, 71.9,
71.6, 67.7 (9 ꢂ –CH), 62.0 (C-600), 61.4 (C-60), 55.7
(2 ꢂ –OCH3), 42.6 (C-1), 20.7 and 20.4 (7 ꢂ –OCOCH3);
ESIMS: m/z 699 (M+Na)+; HRMS m/z: calcd for
C40H47O18, 815.27624; found, 815.28032.
J4 ,5 9.9 Hz, J5 ;6 a 4.5 Hz, J5 ;6 b 2.1 Hz, H-50), 3.02 (dd,
0
0
0
0
0
0
0
1H, J1b;1 7.5 Hz, J1a,1b 16.8 Hz, H-1b), 2.68 (dd, 1H,
0
J1a;1 4.6 Hz J1a,1b 16.8 Hz, H-1a), 2.02–1.98 (4s, 12H,
4 ꢂ –OCOCH3). 13C NMR (50 MHz, CDCl3): d 195.3
(C@O, C-2), 170.7 and 169.9 (4 ꢂ ꢀOCOCH3), 149,
140, 136, 134, 130, 128, 125, 122, 75.8 (C-50), 73.3 (C-
10), 72.5 (C-30), 70.4 (C-20), 66.3 (C-40), 62.9 (C-60),
42.5 (C-1), 21.02 and 20.9 (4 ꢂ –OCOCH3); ESIMS:
m/z 544 (M+Na)+; HRMS m/z: calcd for
C24H27NO12, 521.1533; found, 521.1541.
4.5.2. (E)-1-(20,30,60,200,300,400,600-Hepta-O-acetyl-b-cello-
biosyl)-4-(2-napthyl)but-3-en-2-one
(18). Compound
4.5. (E)-1-(20,30,60,200,300,400,600-Hepta-O-acetyl-b-cello-
biosyl)-4-phenylbut-3-en-2-one (16)
18 was obtained by the reaction of b-glycosylic ketone
15 (1 g, 1.47 mmol) and 2-napthaledehyde (0.23 g,
1.47 mmol) as a colorless solid: mp 220–222 °C; yield
25
Compound 16 was obtained by the reaction of b-gly-
cosylic ketone 15 (1.5 g, 2.22 mmol) and benzaldehyde
(0.228 mL, 2.22 mmol) as a colorless solid: mp 164–
165 °C; yield 1.2 g (71%); Rf 0.5 (3:2 hexane–EtOAc);
0.85 g (70%); Rf 0.5 (3:2 hexane–EtOAc); ½aꢁD ꢀ24 (c
0.1, CHCl3); IR (KBr) mmax cmꢀ1 3021, 2927, 1749,
1
1608; H NMR (300 MHz, CDCl3 + CCl4): d 7.96 (s,
1H, Ar-H), 7.87–7.83 (m, 3H, Ar-H), 7.72–7.66 (m,
2H, Ar-H), 7.54–7.51 (m, 2H, Ar-H, H-4), 7.40–7.37
(m, 3H, Ar-H), 6.84 (d, 1H, J 16.1 Hz, H-3), 5.20 (t,
1H, J 9.2 Hz, H-30), 5.15–5.06 (m, 2H, H-300, H-400),
4.95–4.88 (m, 2H, H-20, H-200), 4.53 (d, 1H, J 7.6 Hz,
H-100), 4.43–4.36 (m, 2H, H-60b, H-60a), 4.15–4.02 (m,
3H, H-600b, H-600a, H-10), 3.77 (t, 1H, J 9.5 Hz, H-40),
25
½aꢁD ꢀ20 (c 0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2959,
1
1747, 1684, 1611; H NMR (300 MHz, CDCl3 + CCl4):
d 7.57–7.47 (m, 3H, Ar-H, H-4), 7.40–7.37 (m, 3H, Ar-
H), 6.70 (d, 1H, J 16.2 Hz, H-3), 5.20 (t, 1H, J 9.2 Hz,
H-30), 5.09 (t, 1H, J 9.0 Hz, H-300), 5.05 (t, 1H, J
9.4 Hz, H-400), 4.95–4.87 (m, 2H, H-20, H-200), 4.49 (d,
1H, J 7.9 Hz, H-100), 4.42–4.34 (m, 2H, H-60b, H-60a),
4.13–4.02 (m, 3H, H-600b,H-600a, H-10), 3.75 (t, 1H, J
9.7 Hz, H-40), 3.67–3.63 (m, 2H, H-500, H-50), 2.93 (dd,
3.67–3.64 (m, 2H, H-500, H-50), 2.93 (dd, 1H, J1b;1
8.4 Hz, J1a,1b 16.0 Hz, H-1b), 2.65 (dd, 1H, J1a;1
0
0
3.1 Hz J1a,2b 16.0 Hz, H-1a), 2.09–2.02 (7s, 21H, 7 ꢂ
–OCOCH3). 13C NMR (50 MHz, CDCl3): d 195.9
(C@O, C-2), 170.6 and 169.1, (7 ꢂ –OCOCH3), 143.8
(C-4), 134.6, 133.7, 132.1 (Ar-C), 131.0 (C-3), 129.2
and 123.8, (7 ꢂ –ArCH), 101.1 (C-100), 78.6, 78.3, 78.2,
77.5, 77.4, 77.3, 77.1, 73.4, 72.3, 68.2, 62.5 (C-600), 61.9
(C-60), 43.2 (C-1), 21.04 and 20.9 (7 ꢂ –OCOCH3);
ESIMS: m/z 837 (M+Na)+; HRMS m/z: calcd for
C38H49NO20, 825.28172; found, 825.28334.
0
1H, J1b;1 8.4 Hz, J1a,1b 16.0 Hz, H-1b), 2.65 (dd, 1H,
0
J1a;1 3.1 Hz J1a,2b 16.0 Hz, H-1a), 2.08–1.96 (7s, 21H,
7 ꢂ –OCOCH3). 13C NMR (50 MHz, CDCl3): d 196.0
(C@O, C-2), 170.9 and 169.4, (7 ꢂ –OCOCH3), 143.9
(C-4), 134.6 (Ar-C) 131.0 (C-3), 129.9 and 126.6,
(5 ꢂ ArCH), 101.0 (C-100), 77.4, 77.2, 77.1, 74.4, 74.2,
73.4, 72.3, 71.9, 68.2, 62.5 (C-600), 62.0 (C-60), 43.1 (C-
1), 21.04 and 20.9 (7 ꢂ –OCOCH3); ESIMS: m/z 787
(M+Na)+; HRMS m/z: calcd for C36H45O18,
765.26059; found, 765.26519.
4.5.1.
(E)-1-(20,30,60,200,300,400,600-Hepta-O-acetyl-b-cello-
Acknowledgments
biosyl)-4-(3,4-dimethoxyphenyl)but-3-en-2-one (17). Com-
pound 17 was obtained by the reaction of b-glycosylic
ketone 15 (1 g, 1.47 mmol) and 3,4-dimethoxybenzalde-
hyde (0.245 g, 1.47 mmol) as a colorless solid: mp 160–
161°C; yield 0.9 g (67%); Rf 0.4 (2:3 hexane–EtOAc);
This is a CDRI Communication No. 7467. We are
thankful to Director CDRI for his keen interest in this
program. S.S.B., J.P., and A.S. thanks CSIR, New Delhi
for their SRF and JRF, respectively. Financial assis-
tance from DRDO New Delhi and DBT New Delhi is
also gratefully acknowledged (ERIP/ER/0502127/M/
01/857).
25
½aꢁD ꢀ25 (c 0.1, CHCl3); IR (KBr) mmax cmꢀ1: 2929,
1749, 1641; 1H NMR (300 MHz, CDCl3 + CCl4): d
7.45 (d, 1H, J 16.0 Hz, H-4), 7.09 (d, 1H, J 8.2 Hz,

1406
S. S. Bisht et al. / Carbohydrate Research 343 (2008) 1399–1406
14. Du, Y.; Linhardt, R. J.; Vlahov, I. R. Tetrahedron 1998,
Supplementary data
54, 9913–9959.
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