Synthesis and enzyme inhibitory activities of highly functionalized pyridylmethyl-C-β-D-Glycosides

Article abstract of DOI:10.1080/07328303.2011.618280

Several pyridylmethyl-C-β-D-glycosides (3a-3l, 6a, and 6h) were synthesized by refluxing 3-(β-D-glucopyranosyl)/(β-D-cellobiosyl)- propanones and dicyanobenzylidenes with ammonium acetate in anhydrous toluene in moderate to good yields. The reaction invol

Full text of DOI:10.1080/07328303.2011.618280

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Synthesis and Enzyme Inhibitory
Activities of Highly Functionalized
Pyridylmethyl-C-β-D-Glycosides
Vivek Parashar Pandey a , Natasha Jaiswal b , A. K. Srivastava b
Sanjeev K. Shukla c & Rama Pati Tripathi a
,
a Medicinal and Process Chemistry Division , Central Drug Research
Institute (CSIR-CDRI) , Lucknow, 226001, India
b Biochemistry Division , Central Drug Research Institute (CSIR-
CDRI) , Lucknow, 226001, India
c Sophisticated Instrumentation and Analytical Facility Division ,
Central Drug Research Institute (CSIR-CDRI) , Lucknow, 226001, India
Published online: 17 Oct 2011.
To cite this article: Vivek Parashar Pandey , Natasha Jaiswal , A. K. Srivastava , Sanjeev K. Shukla
& Rama Pati Tripathi (2011) Synthesis and Enzyme Inhibitory Activities of Highly Functionalized
Pyridylmethyl-C-β-D-Glycosides, Journal of Carbohydrate Chemistry, 30:3, 132-146, DOI:
10.1080/07328303.2011.618280
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Journal of Carbohydrate Chemistry, 30:132–146, 2011
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ISSN: 0732-8303 print / 1532-2327 online
DOI: 10.1080/07328303.2011.618280
Synthesis and Enzyme
Inhibitory Activities of Highly
Functionalized Pyridylmethyl-
C-β-D-Glycosides
Vivek Parashar Pandey,1 Natasha Jaiswal,2 A. K. Srivastava,2
Sanjeev K. Shukla,3 and Rama Pati Tripathi1
1Medicinal and Process Chemistry Division, Central Drug Research Institute
(CSIR-CDRI), Lucknow-226001, India
2Biochemistry Division, Central Drug Research Institute (CSIR-CDRI),
Lucknow-226001, India
3Sophisticated Instrumentation and Analytical Facility Division, Central Drug
Research Institute (CSIR-CDRI), Lucknow-226001, India
Several pyridylmethyl-C-β-D-glycosides (3a–3l, 6a, and 6h) were synthesized by reflux-
ing 3-(β-D-glucopyranosyl)/(β-D-cellobiosyl)-propanones and dicyanobenzylidenes with
ammonium acetate in anhydrous toluene in moderate to good yields. The reaction in-
volves a C C Michael addition of enamine, formed from glycosyl ketone and ammonium
acetate, to the dicayanobenzylidene derivative; subsequent dehydrative cyclization; and
oxidative aromatization. Two of these prototypes, compounds 3e and 3k, were deacety-
lated to the respective glucopyranosyl methyl pyridines 4e and 4k with NaOMe/MeOH.
The synthesized compounds were screened for their in vitro α-glucosidase inhibitory ac-
tivities and one of the compounds showed 20% inhibition as compared to standard drug
acarbose displaying 39% inhibition.
Keywords Pyridylmethyl-C-β-D-glycosides; Michael addition; Knovenagel condensa-
tion; Malononitrile; α-Glucosidase inhibitors
INTRODUCTION
The study on sugar heterocycles is gaining momentum in organic synthe-
ses due to their chemotherapeutic potential and as glycohybrids in chemical
biology.[1] The sugar residues in such molecules offer several advantages to
Received March 18, 2011; accepted August 24, 2011.
Address correspondence to Rama Pati Tripathi, Medicinal and Process Chemistry Di-
vision, Central Drug Research Institute (CSIR-CDRI), Lucknow-226001, India. E-mail:
rpt.cdri@gmail.com; rp tripathi@cdri.res.in
132

Highly Functionalized Pyridylmethyl-C-β-D-Glycosides
133
elucidate the required biological response. In general, sugars as glycol-
conjugates are very important in most of the intercellular and intracellular
events and form the basis of molecular recognition in biological events. In
chemotherapeutic glycosides the sugar components impart the water solubility
and good pharmacokinetic parameters[2] and reduce the toxicity of aglycon,[3] if
any. A number of glycosyl heterocyles have been synthesized, keeping in view
the diverse range of biological activities associated with these molecules.[4–14]
A
few of the important glycopyranosyl heterocyles such as oxadiazoles,[4–6] tetra-
zoles,[6,7] benzothiazoles,[6,8] and benzimidazoles[6,9] exhibit glucosidase and/or
glycogen phosphorylase inhibitory activities. The glycosidic linkage between
the sugar and heterocyles may be of C C, C N, or C O and generally ex-
ist in two forms, α- and β-, depending on the orientation of aglycon at the
anomeric carbon. C C glycosidic linkage in glycosides is more stable than
that of C N or C O glycosidic linkage and therefore is less amenable for
hydrolysis. A number of naturally occurring and synthetic compounds with a
pyridine scaffold possess interesting pharmacological properties.[10–12] Among
them, 2-amino-3-cyanopyridines have been identified as IKK-β inhibitors[13,14]
and possess a number of biological activities. Besides, they are important and
useful intermediates in preparing a variety of heterocyclic compounds.[15–17]
Several aryl and heteroaryl-β-C-glycosides are potent clinical/preclinical can-
didates for the treatment of diabetes as renal sodium-dependent glucose co-
transporter-2 (SGLT2) inhibitors.[18,19] Besides the above chemotherapeutic
potential, the pyridyl glycosides have recently been developed as chiral ligands
in various asymmetric reactions.[20] Keeping in view the above, and in continu-
ation of a program toward the development new antidiabetic agents from aryl-
C-glycosides, we were interested in synthesizing pyridine-based C-glycosides
as chemotherapeutic agents and as chiral ligands for other applications.
RESULTS AND DISCUSSION
The starting glycosyl ketone (1) was prepared as reported earlier by us and oth-
ers by reaction of D-glucose with acetyl acetone in aqueous basic medium.[21,22]
The dicayanobenzylidene derivatives (2a–2l) were prepared by Knovenagel
condensation of malononitrile and aromatic aldehydes in ethanolic KOH as
reported earlier.[23] The starting glycosyl ketone and benzylidenes were char-
acterized on the basis of their spectroscopic data.
To start with, reaction of the 3-(2,3,4,6-tri-O-acetyl-β-D-glucopyranosyl)-
propanone (1) with 1,1-dicyano-2-naphylidene (2a) and ammonium acetate in
toluene under reflux led to the formation of many products (TLC) from which
we could isolate a pure crystalline compound (3a) by column chromatogra-
phy. The structure of compound (3a) was established as 2-amino-3-cyano-4-(2ꢁ-
naphthyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-glucopyranosyl)methyl] pyridine
based on its spectroscopic data and microanalysis. The IR spectrum

V. P. Pandey et al.
134
exhibited absorption band at 1751 cm−1 indicating the carbonyl group of the
sugar acetyl groups, while an absorption band at 2204 cm−1 indicated the
presence of a cyano ( CN) group. ESMS of the compound displayed m/z 590
[M+H]+ peak. In the 1H NMR spectrum the aromatic protons were observed as
singlets, doublets, and multiplets in the usual range of δ 8.09 to 6.78 ppm. The
pyridyl ring proton appeared as a singlet at δ 6.78. Two exchangeable protons
of the NH2 group appeared as a singlet at δ 5.39 ppm as evidenced by D2O
shake. The H-3ꢁꢁof the sugar ring appeared as a triplet at δ 5.23 (t, 1H, J =
9.21 Hz) and H-2ꢁꢁand H-4ꢁꢁ as a multiplet in the range of δ 5.08 to 4.97. The
H-6aꢁꢁ of the sugar moiety was observed as a doublet of doublet at δ 4.24 (dd,
1H, J1 = 5.01 Hz, J2 = 12.21 Hz, H-6aꢁꢁ), while H-6bꢁꢁ and H-1ꢁꢁ were visible
as a multiplet in the range of δ 4.07 to 3.95. Further, H-5ꢁꢁ was observed as a
multiplet in the range of δ 3.66 to 3.62. The protons of the four sugar acetyl
groups ( OCOCH3) were visible as four singlets in the range of δ 2.02 to 1.98.
In 13C NMR spectrum the signal for C N carbon was visible at δ 115.0. The
aromatic and heteroaromatic carbons were observed at their usual chemical
shifts in the range of δ 170.1 to 88.1, while the pyranose sugar carbons C-1ꢁꢁ,
C-2ꢁꢁ, C-3ꢁꢁ, C-4ꢁꢁ, and C-5ꢁꢁ appeared at δ 76.7, 75.8, 74.3, 71.8, and 68.5. The
two methylene carbons OCH2 and CH2 were observed at δ 61.9 and 40.5,
respectively. The four methyl carbons of the acetyl groups were observed at δ
20.6, 20.5, 20.5, and 20.4, respectively.
Similarly, reactions of other dicyanoarylidenes (2b–2l) with the above
glycosyl ketone 1 separately led to the formation of respective 4-arylpyridyl
methyl glycosides (3b–3l) (Sch. 1, Table 1) in moderate yields. The deacety-
lation of the protecting groups (acetyl) in two of the compounds synthesized
above, 3e and 3k, with NaOMe/MeOH led to the formation of pyridylmethyl-β-
D-glucopyranosides 4e and 4k, respectively, in good yields (Sch. 1). Structures
of all the synthesized compounds were established on the basis of their spectro-
scopic data (IR, 1H and 13C NMR, and ESMS) and microanalyses. The IR spec-
tra of the products (3a–3l) showed the characteristic absorption bands in the
Scheme 1: Synthesis of 2-amino-3-cyano-4-aryl-6-(β-glucopyranosyl)methyl pyridine
derivatives (3a–3l) and (4e, 4k).

Highly Functionalized Pyridylmethyl-C-β-D-Glycosides
135
Table 1: Synthesis of 2-amino-3-cyano-4-aryl-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3a–3l) and 2-amino-3-cyano-aryl-6-[(β-D-glucopyr
anosyl)methyl]pyridine (4e, 4k)
Ar
Compound no.
Time (h)
Yield (%)∗
2-Naphthyl
3a
3b
3c
3d
3e
3f
14
14
16
18
16
18
15
18
16
18
15
14
0.5
0.5
35
42
16
36
40
29
40
32
43
51
28
53
58
52
4-Methoxyphenyl
Phenyl
3-Pyridyl
4-Bromophenyl
4-Nitrophenyl
3,4-Dimethoxyphenyl
4-Benzyloxyphenyl
4-Fluorophenyl
4-N,N-Dimethylphenyl
2-Thienyl
3g
3h
3i
3j
3k
3l
4-Chlorophenyl
4-Bromophenyl
2-Thienyl
4e
4k
∗Refers to yield isolated by column chromatography.
region 2143 to 2213 cm−1 due to the C N stretching and around 1740 cm−1
1
due to the carbonyl of the acetyl groups. In H NMR spectra, the singlets
in the range of δ 7.62 to 6.61 ppm indicated the pyridyl ring proton, and a
characteristic singlet in the region around δ 5.25 to 5.44 ppm accounted for
two protons of the amino group ( NH2) as a pyridyl ring substituent. The
rest of the aromatic and aliphatic protons appeared at their usual chemical
shifts. In one of the compounds, 3i, having a 4ꢁ-fluorophenyl substituent in
1
the pyridine ring, we have observed the C and F couplings [163.9 (d, JCF
=
250.6 Hz, C-4ꢁ, 132.6 (d, 4JCF = 3.2 Hz, C-1ꢁ), 130.4 (d, 3JCF = 8.5 Hz, C-2ꢁ,6ꢁ),
116.3 (d, 2JCF = 21.7 Hz, C-3ꢁ,5ꢁ)], in accordance with the standard values. The
mass spectra of the compounds were also in agreement with their molecular
formulae.
Finally, to probe the scope of the above reaction, we explored the reaction
of 3-(β-D-cellobiosyl)-propanone (5) with dicyanobenzylidene derivatives (2a
and 2h) and ammonium acetate under the conditions as described above. The
2-amino-4-aryl-3-cyano-pyridylmethylidene peracetylated β-D-C-cellobiosides
6a and 6h were obtained, respectively, in good yields (Sch. 2). The structures
of these compounds were also established on the basis of their spectroscopic
data and microanalyses.
All the above synthesized compounds were screened against α-glucosidase
enzyme,[24,25] a well-known target to treat type 2 diabetes. For the assay,
100 µM of the synthesized compounds dissolved in DMSO were evaluated for
their inhibitory potential against the α-glucosidase enzyme. The percentage of
inhibition was calculated with respect to control acarbose, clinically used for

V. P. Pandey et al.
136
Scheme 2: Synthesis of 2-amino-3-ayano-4-aryl-6-[(2ꢁꢁ,3ꢁꢁ,6ꢁꢁ,2ꢁꢁꢁ,3ꢁꢁꢁ,4ꢁꢁꢁ,6ꢁꢁꢁ-hepta-O-acetyl-
β-cellobiosyl)methyl]pyridine (6a, 6h).
diabetes. The enzyme inhibitory data of screened compounds are shown in
Table 2.
The compounds, in general, exhibited 2% to 21% inhibition of α-glucosidase
enzyme as compared to standard drug, acarbose, displaying 39% inhibition. As
evident from the activity results (Table 2) among all the compounds screened,
β-D-glucopyranosylmethyl pyridine (3h) and β-D-cellobiosylmethyl pyridine
(6h) having 4-benzyloxyphenyl substituent in the pyridine ring displayed good
inhibitory activities (21% and 20% inhibition, respectively) as compared to the
standard drug. Since these compounds did not exhibit significant inhibition, no
definite structure-activity relationship could be established. However, further
work on this series to find out biologically active compounds is currently under
way and will be reported very soon.
In conclusion, we have developed a method for the synthesis of a series
of pyridylmethyl-C-β-D-glycosides (3a–3l and 6a and 6h) from D-glucose and
cellobiose, respectively, in good yields. All the synthesized compounds were
Table 2: α-Glucosidase inhibitory activities of synthesized compounds
Compounds
% Inhibition (at 100 µM)
3a
3b
3c
3d
3e
3f
−9.44
+12.7
−1.73
+13.7
+3.37
−2.44
0.00
−21.00
−3.67
−7.51
−9.44
−7.51
+1.05
+5.69
+2.21
−20.00
−39.00
3g
3h
3i
3j
3k
3l
4e
4k
6a
6h
Acarbose

Highly Functionalized Pyridylmethyl-C-β-D-Glycosides
137
screened for their antidiabetic activities targeting α-glucosidase, a well-known
enzyme target to treat type 2 diabetes. Only one of the compounds showed mild
inhibition of the enzyme.
EXPERIMENTAL
General Procedures
Commercially available reagent-grade chemicals were used as received.
All reactions were followed by TLC on E. Merck Kieselgel 60 F254, with de-
tection by UV light, spraying a 20% KMnO4 aq. solution and/or spraying a 4%
H2SO4 ethanolic solution. Column chromatography was performed on silica gel
(60–120 mesh E. Merck). IR spectra were recorded as thin films or on KBr pel-
lets with a Perkin Elmer Spectrum RX-1 (4000–450 cm−1) spectrophotometer.
1H and 13C NMR spectra were recorded on a Brucker 400/300/200 in CDCl3,
CDCl3+CCl4, CD3OD, or DMSO-d6. Chemical shift values are reported in ppm
relative to TMS (tetramethylsilane) as internal reference, unless otherwise
stated; s (singlet), d (doublet), dd (double doublet), m (multiplet); J in hertz.
ESI mass spectra were performed using Quattro II (Micromass). Elemental
analyses were performed on a Perkin–Elmer 2400 II elemental analyzer. Op-
tical rotations were measured in a 1.0 dm tube with a Rudolph Autopol III
polarimeter in CHCl3 or MeOH.
General Procedure for the Preparation of 2-Amino-3-cyano-4-
aryl-6-[(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,6ꢀꢀ-tetra-O-acetyl-β-D-glucopyranosyl)
methyl]pyridine (3a–3l)
To a stirring solution of one of the selected benzylidenemalanonitriles
(2a–2l) (1.0 mmol) and 3-(β-D-pyranosyl)-propanone 1 (1.0 mmol) in toluene
(10 mL) was added ammonium acetate (1.5 mmol). Reaction mixture was re-
fluxed till the disappearance of substrate 1 (TLC). Now, the reaction mix-
ture was evaporated under reduced pressure. The residue was extracted with
EtOAc/water (7:3, v:v) and the organic layer was dried (Na2SO4) and concen-
trated under reduced pressure to give a crude mass. The latter was purified
by column chromatography on silica gel (60–120 mesh) using EtOAc:hexane
as eluent to give corresponding 2-amino-3-cyano-4-aryl-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-
acetyl-β-D-glucopyranosyl) methyl]pyridine (3a–3l).
2-Amino-3-cyano-4-(2ꢁ-naphthyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3a)
It was obtained as pale yellow solid; m.p. 148–152◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −25.03 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2204 (C N

V. P. Pandey et al.
138
1
stretching), 1751 (O C O stretching); H NMR (300 MHz, CDCl3) δ = 8.09
(s, 1H, ArH), 7.97 (m, 3H, ArH), 7.68 (d, 2H, J = 8.25 Hz, ArH), 7.56 (m, 2H,
ArH), 6.78 (s, 1H, ArH), 5.39 (s, 2H, NH2), 5.23 (t, 1H, J = 9.21 Hz, H-3ꢁꢁ),
5.08–4.97 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ), 4.24 (dd, 1H, J1 = 5.01 Hz, J2 = 12.21 Hz, H-
6aꢁꢁ), 4.07–3.95 (m, 2H, H-1ꢁꢁ, H-6bꢁꢁ), 3.66–3.62 (m, 1H, H-5ꢁꢁ), 2.91 (d, 2H, J =
5.7 Hz, CH2), 2.02–1.88 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ =
170.1, 170.0, 169.4, 169.1, 160.7, 160.1, 154.3, 133.7, 133.0, 128.7, 128.6, 128.0,
127.7, 127.2, 126.7, 125.2, 116.7, 115.0 (CN), 88.1, 76.7 (CH), 75.8 (CH), 74.3
(CH), 71.8 (CH), 68.5 (CH), 61.9 (OCH2), 40.5 (CH2), 20.6, 20.5, 20.5, 20.4;
Anal calcd for C31H31N3O9: C, 63.15; H, 5.30; N, 7.13; found C, 63.18; H, 5.35;
N, 7.09; ESMS m/z = 590(M+H)+.
2-Amino-3-cyano-4-(4ꢁ-methoxyphenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranoyl)methyl]pyridine (3b)
It was obtained as yellow solid; m.p. 160–164◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 11.28 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2208 (C N
stretching), 1752 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 7.57 (d,
2H, J = 8.64 Hz, ArH), 7.01 (d, 2H, J = 8.64 Hz, ArH), 6.63 (s, 1H, ArH), 5.28
(s, 2H, NH2), 5.20 (t, 1H, J = 9.24 Hz, H-3ꢁꢁ), 5.06–4.94 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ),
4.24 (dd, 1H, J1 = 4.98 Hz, J2 = 12.21 Hz, H-6aꢁꢁ), 4.03–3.92 (m, 2H, H-1ꢁꢁ,
H-6bꢁꢁ), 3.88 (s, 3H, ArOCH3), 3.63–3.59 (m, 1H, H-5ꢁꢁ), 2.85 (d, 2H, J = 4.38
Hz, CH2), 2.04–1.93 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 169.9,
169.8, 169.2, 168.2, 161.0, 160.4, 160.1, 153.8, 129.5, 128.6, 116.8, 114.4 (CN),
114.3, 87.6, 76.7 (CH), 75.8 (CH), 74.2 (CH), 71.8 (CH), 68.4 (CH), 61.8 (OCH2),
55.1 (OCH3), 40.5 (CH2), 20.6, 20.5, 20.5, 20.4; Anal calcd for C28H31N3O10: C,
59.05; H, 5.49; N, 7.38; found C, 59.10; H, 5.53; N, 7.34; ESMS m/z = 570
(M+H)+.
2-Amino-3-cyano-4-(phenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3c)
It was obtained as yellow solid; m.p. 176–180◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −19.57 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2210 (C N
stretching), 1751 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 7.59 (m,
2H, ArH), 7.49 (m, 3H, ArH), 6.66 (s, 1H, ArH), 5.37 (s, 2H, NH2), 5.18 (t, 1H,
J = 9.09 Hz, H-3ꢁꢁ), 5.06–4.94 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ), 4.22 (dd, 1H, J1 = 5.1 Hz,
J2 = 12.24 Hz, H-6aꢁꢁ), 4.04–3.95 (m, 2H, H-1ꢁꢁ, H-6bꢁꢁ), 3.65–3.60 (m, 1H, H-
5ꢁꢁ), 2.87 (d, 2H, J1 = 5.55 Hz, CH2), 2.01–1.90 (12H, 4 × OCOCH3); 13C NMR
(50 MHz, CDCl3) δ = 170.2, 170.0, 169.4, 160.7, 160.0, 154.3, 136.4, 129.8,
128.8, 128.1, 124.4, 116.6, 114.7 (CN), 87.9, 76.3 (CH), 75.7 (CH), 74.2 (CH),
71.7 (CH), 68.4 (CH), 61.9 (OCH2), 40.5 (CH2), 20.6, 20.5, 20.5, 20.4; Anal
calcd for C27H29N3O9: C, 60.11; H, 5.42; N, 7.79; found C, 60.15; H, 5.47; N,
7.75; ESMS m/z = 540 (M+H)+.

Highly Functionalized Pyridylmethyl-C-β-D-Glycosides
139
2-Amino-3-cyano-4-(3ꢁ-pyridyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3d)
It was obtained as pale yellow solid; m.p. 148–152◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −16.85 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2210 (C N
stretching), 1751 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 8.79 (s,
1H, ArH), 8.73 (d, 2H, J = 3.63 Hz, ArH), 7.96 (dd, 1H, J1 = 1.92 Hz, J2 =
6.12 Hz, ArH), 7.46 (dd, 1H, J1 = 4.77 Hz, J2 = 7.47 Hz, ArH), 6.67 (s, 1H,
ArH), 5.44 (s, 2H, NH2), 5.20 (t, 1H, J = 9.33 Hz, H-3ꢁꢁ), 5.06–4.93 (m, 2H,
H-4ꢁꢁ, H-2ꢁꢁ), 4.21 (dd, 1H, J1 = 4.92 Hz, J2 = 7.44 Hz, H-6aꢁꢁ), 4.04–3.93 (m,
2H, H-1ꢁꢁ, H-6bꢁꢁ), 3.63–3.59 (m, 1H, H-5ꢁꢁ), 2.88 (d, 2H, J1 = 5.61 Hz, CH2),
2.02–1.93 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.0, 169.4,
169.1, 161.3, 160.1, 150.7, 148.7, 135.4, 132.3, 123.4, 116.1, 114.5 (CN), 87.7,
76.5 (CH), 75.8 (CH), 74.2 (CH), 71.5 (CH), 68.3 (CH), 61.8 (OCH2), 40.4 (CH2),
20.6, 20.5; Anal calcd for C26H28N4O9: C, 57.77; H, 5.22; N, 10.37; found C,
57.75; H, 5.24; N, 10.38; ESMS m/z = 541 (M+H)+.
2-Amino-3-cyano-4-(4ꢁ-bromophenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl) methyl]pyridine (3e)
It was obtained as pale yellow solid; m.p. 153–157◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −38.60 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2213 (C N
stretching), 1750 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 7.65 (d,
2H, J = 8.16 Hz, ArH), 7.47 (d, 2H, J = 8.16 Hz, ArH), 6.64 (s, 1H, ArH), 5.32
(s, 2H, NH2), 5.24 (t, 1H, J = 9.27 Hz, H-3ꢁꢁ), 5.08–4.95 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ),
4.21 (dd, 1H, J1 = 5.1 Hz, J2 = 12.1 Hz, H-6aꢁꢁ), 4.06–3.96 (m, 2H, H-1ꢁꢁ, H-
6bꢁꢁ), 3.65–3.60 (m, 1H, H-5ꢁꢁ), 2.89 (d, 2H, J1 = 5.5 Hz, CH2), 2.02–1.91 (12H,
4 × OCOCH3); 13C NMR (75 MHz, CDCl3) δ = 170.1, 170.0, 169.4, 169.1, 161.0,
160.1, 153.0, 135.3, 132.1, 129.7, 124.4, 116.4, 114.3 (CN), 87.5, 75.7 (CH), 74.2
(CH), 71.7 (CH), 68.4 (CH), 61.9 (OCH2), 40.4 (CH2), 20.6, 20.5, 20.4, 20.3; Anal
calcd for C27H28BrN3O9: C, 52.44; H, 4.56; Br, N, 6.79; found C, 52.48; H, 4.60;
N, 6.75; ESMS m/z = 619 (M+H)+.
2-Amino-3-cyano-4-(4ꢁ-nitrophenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3f)
It was obtained as light brown solid; m.p. 113–116◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 18.74 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2213 (C N
stretching), 1750 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 7.65 (d,
2H, J = 8.16 Hz, ArH), 7.47 (d, 2H, J = 8.16 Hz, ArH), 6.64 (s, 1H, ArH), 5.32
(s, 2H, NH2), 5.24 (t, 1H, J = 9.27 Hz, H-3ꢁꢁ), 5.08–4.95 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ),
4.21 (dd, 1H, J1 = 5.10 Hz, J2 = 12.12 Hz, H-6aꢁꢁ), 4.06–3.97 (m, 2H, H-1ꢁꢁ,
H-6bꢁꢁ), 3.65–3.61 (m, 1H, H-5ꢁꢁ), 2.89 (d, 2H, J1 = 5.52 Hz, CH2), 2.02–1.91
(12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.1, 170.0, 169.4, 169.1,
161.2, 161.0, 160.1, 153.0, 135.3, 132.1, 129.7, 124.4, 116.4, 114.3 (CN), 87.5,

V. P. Pandey et al.
140
75.7 (CH), 74.2 (CH), 71.71 (CH), 68.4 (CH), 61.9 (OCH2), 40.4 (CH2), 20.6,
20.5, 20.5, 20.4; Anal calcd for C27H28N4O11: C, 55.48; H, 4.83; N, 9.58; found
C, 55.52; H, 4.87; N, 9.52; ESMS m/z = 585 (M+H)+.
2-Amino-3-cyano-4-(3ꢁ,4ꢁ-dimethoxyphenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3g)
It was obtained as yellow solid; m.p. 160–164◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −16.47 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2208 (C N
1
stretching), 1752 (O C O stretching); H NMR (300 MHz, CDCl3) δ = 7.17
(s, 1H, ArH), 6.94 (m, 2H, ArH), 6.61 (s, 1H, ArH), 5.39 (s, 2H, NH2), 5.20
(t, 1H, J = 9.24 Hz, H-3ꢁꢁ), 5.06–4.94 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ), 4.24 (dd, 1H, J1 =
4.98 Hz, J2 = 12.21 Hz, H-6aꢁꢁ), 4.03–3.92 (m, 1H, H-6bꢁꢁ), 4.01–3.89 (m, 7H,
H-1ꢁꢁ, ArOCH3), 3.60–3.57 (m, 1H, H-5ꢁꢁ), 2.83 (d, 2H, J = 4.92 Hz, CH2),
2.01–1.89 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.6, 169.8,
169.7, 169.2, 168.8, 160.4, 160.2, 153.9, 150.6, 149.2, 128.8, 121.0, 116.9, 114.3
(CN), 111.4, 111.3, 87.5, 76.3 (CH), 75.8 (CH), 74.2 (CH), 71.8 (CH), 68.5 (CH),
61.8 (OCH2), 55.8 (OCH3), 55.7 (OCH3) 40.5 (CH2), 20.5, 20.4, 20.3; Anal calcd
for C29H33N3O11: C, 58.09; H, 5.55; N, 7.01; found C, 58.12; H, 5.58; N, 6.98;
ESMS m/z = 600 (M+H)+.
2-Amino-3-cyano-4-(4ꢁ-benzyloxyphenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3h)
It was obtained as pale yellow solid; m.p. 168–172◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −21.77 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2143 (C N
1
stretching), 1746 (O C O stretching); H NMR (300 MHz, CDCl3) δ = 7.58
(d, 2H, J = 8.58 Hz, ArH), 7.47 (m, 5H, ArH), 7.11 (d, 2H, J = 8.58 Hz, ArH),
6.65 (s, 1H, ArH), 5.26 (m, 3H, NH2, H-3ꢁꢁ), 5.14 (s, 2H, OCH2), 5.09–4.97 (m,
2H, H-4ꢁꢁ, H-2ꢁꢁ), 4.23 (dd, 1H, J1 = 5.16 Hz, J2 = 12.18 Hz, H-6aꢁꢁ), 4.06–3.95
(m, 2H, H-1ꢁꢁ, H-6bꢁꢁ), 3.67–3.63 (m, 1H, H-5ꢁꢁ), 2.88 (d, 2H, J = 5.43 Hz, CH2),
2.03–1.90 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.5, 170.3,
169.7, 169.4, 160.6, 160.2, 160.1, 153.9, 136.4, 134.8, 129.6, 128.9, 128.6, 128.1,
127.4, 117.2, 115.2, 114.59 (CN), 87.5, 75.7 (CH), 74.3 (CH), 70.1 (OCH2Ph),
71.8 (CH), 68.5 (CH), 62.0 (OCH2), 40.6 (CH2), 20.6, 20.6, 20.5; Anal calcd for
C34H35N3O10: C, 63.25; H, 5.46; N, 6.51; found C, 63.28; H, 5.50; N, 6.49; ESMS
m/z = 646 (M+H)+.
2-Amino-3-cyano-4-(4ꢁ-fluorophenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3i)
It was obtained as yellow solid; m.p. 181–184◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −21.68 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2204 (C N
stretching), 1751 (O C O stretching); 1H NMR (400 MHz, CDCl3) δ = 7.58 (m,

Highly Functionalized Pyridylmethyl-C-β-D-Glycosides
141
2H, ArH-2ꢁ,6ꢁ), 7.19 (m, 2H, ArH-3ꢁ,5ꢁ), 6.64 (s,1H, ArH-5), 5.39 (s, 2H, NH2),
5.21 (t, 1H, J = 9.4 Hz, H-3ꢁꢁ), 5.07–4.96 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ), 4.18 (dd, J1 =
5.1 Hz, J2 = 12.5, 1H, H-6aꢁꢁ), 4.06–3.95 (m, 2H, H-6bꢁꢁ, H-1ꢁꢁ), 3.65 (m, 1H,
H-5ꢁꢁ), 2.88 (d, 2H, J = 5.7 Hz, CH2), 2.02–1.90 (12H, 4xOCOCH3); 13C NMR
1
(100 MHz, CDCl3) δ = 170.6, 170.5, 169.9 & 169.6 (4 × CO), 163.9 (d, JCF
=
250.6 Hz, C-4ꢁ), 161.0 (C-6), 160.2 (C-2), 153.6 (C-4), 132.6 (d, JCF = 3.2 Hz,
4
C-1ꢁ), 130.4 (d, JCF = 8.5 Hz, C-2ꢁ,6ꢁ), 116.8 (CN), 116.3 (d, JCF = 21.7 Hz,
C-3ꢁ,5ꢁ), 114.9 (C-5), 88.0 (C-3), 76.7 (C-1ꢁꢁ), 75.9 (C-5ꢁꢁ), 74.4 (C-3ꢁꢁ), 71.9 (C-2ꢁꢁ),
68.8 (C-4ꢁꢁ), 62.3 (OCH2-6ꢁꢁ), 40.6 (CH2), 20.9, 20.8, 20.7 and 20.6 (4 × CH3);
Anal calcd for C27H28FN3O9: C, 58.17; H, 5.06; N, 7.54; found C, 58.20; H, 5.10;
N, 7.50; ESMS m/z = 558 (M+H)+.
3
2
2-Amino-3-cyano-4-(4ꢁ-N,N-dimethylphenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3j)
It was obtained as orange solid; m.p. 139–142◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]2D5 −27.06 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2207 (C N
stretching), 1748 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 7.54 (d,
2H, J = 8.82 Hz, ArH), 6.77 (d, 2H, J = 8.82 Hz, ArH), 6.62 (s, 1H, ArH), 5.25
(s, 2H, NH2), 5.21 (t, 1H, J = 9.42 Hz, H-3ꢁꢁ), 5.06–4.95 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ),
4.23 (dd, 1H, J1 = 6.54 Hz, J2 = 12.12 Hz, H-6aꢁꢁ), 4.10–3.96 (m, 2H, H-1ꢁꢁ,
H-6bꢁꢁ), 3.64–3.60 (m, 1H, H-5ꢁꢁ), 3.04 (s, 6H, ArN(CH3)2), 2.85 (d, 2H, J = 3.72
Hz, CH2), 2.02–1.91 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.2,
170.0, 169.4, 169.1, 160.1, 159.7, 154.4, 151.4, 129.3, 123.4, 114.0 (CN), 112.3,
111.9, 87.0, 76.5 (CH), 75.7 (CH), 74.2 (CH), 71.7 (CH), 68.6 (CH), 62.0 (OCH2),
40.5, 40.3, 40.1 (CH2), 20.6, 20.5, 20.5, 20.4; Anal calcd for C29H34N4O9: C,
59.79; H, 5.88; N, 9.62; found C, 59.83; H, 5.93; N, 9.67; ESMS m/z = 583
(M+H)+.
2-Amino-3-cyano-4-(thio-2-nyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3k)
It was obtained as gray solid; m.p. 189–192◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]D = −24.73 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2208 (C N
1
stretching), 1746 (O C O stretching); H NMR (300 MHz, CDCl3+CD3OD)
δ = 7.81 (d, 2H, J = 3.15 Hz, ArH), 7.56 (d, 1H, J = 4.80 Hz, ArH), 7.20 (m,
1H, ArH), 6.76 (s, 1H, ArH), 5.18 (t, 1H, J = 9.21 Hz, H-3ꢁꢁ), 5.06–4.96 (m, 2H,
H-4ꢁꢁ, H-2ꢁꢁ), 4.25 (dd, 1H, J1 = 5.16 Hz, J2 = 12.36 Hz, H-6aꢁꢁ), 4.03–3.90 (m,
2H, H-1ꢁꢁ, H-6bꢁꢁ), 3.65–3.62 (m, 1H, H-5ꢁꢁ), 2.84 (d, 2H, J = 5.70 Hz, CH2),
2.07–1.92 (12H, 4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.3, 170.2,
169.6, 169.3, 161.0, 160.1, 153.1, 136.1, 134.8, 129.4, 129.2, 116.5, 114.5 (CN),
87.6, 76.5(CH), 75.7 (CH), 74.2 (CH), 71.7 (CH), 68.5 (CH), 62.1 (OCH2), 40.5
(CH2), 20.6, 20.5, 20.5, 20.4; Anal calcd. for C25H27N3O9S: C, 55.04; H, 4.99; N,
7.70; found C, 55.08; H, 4.96; N, 7.73; ESMS m/z = 546 (M+H)+.

V. P. Pandey et al.
142
2-Amino-3-cyano-4-(4ꢁ-chlorophenyl)-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-acetyl-β-D-
glucopyranosyl)methyl]pyridine (3l)
It was obtained as pale yellow solid; m.p. 150–153◦C; Rf 0.5 (2:98, MeOH:
CHCl3); [α]D = −21.50 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 2209 (C N
stretching), 1752 (O C O stretching); 1H NMR (300 MHz, CDCl3) δ = 7.54 (d,
2H, J = 8.40 Hz, ArH), 7.48 (m, 2H, J = 8.30 Hz, ArH), 6.63 (s, 1H, ArH), 5.34
(s, 2H, NH2), 5.24 (t, 1H, J = 9.27 Hz, H-3ꢁꢁ), 5.08–4.95 (m, 2H, H-4ꢁꢁ, H-2ꢁꢁ),
4.21 (dd, 1H, J1 = 5.01 Hz, J2 = 12.48 Hz, H-6aꢁꢁ), 4.06–3.93 (m, 2H, H-1ꢁꢁ, H-
6bꢁꢁ), 3.65–3.61 (m, 1H, H-5ꢁꢁ), 2.88 (d, 2H, J = 5.55 Hz, CH2), 2.02–1.91 (12H,
4 × OCOCH3); 13C NMR (50 MHz, CDCl3) δ = 170.3, 170.2, 169.6, 169.3, 161.0,
160.1, 153.1, 136.1, 134.8, 129.4, 129.2, 116.5, 114.5 (CN), 87.6, 76.5 (CH), 75.7
(CH), 74.2 (CH), 71.7 (CH), 68.5 (CH), 62.0 (OCH2), 40.5 (CH2), 20.6, 20.5, 20.5,
20.4; Anal calcd. for C27H28ClN3O9: C, 56.50; H, 4.92; N, 7.32; found C, 56.56;
H, 4.96; N, 7.28; ESMS m/z = 574 (M+H)+.
General Procedure for Synthesis of Compounds (4e) and (4k)
To a stirring solution of 2-amino-3-cyano-4-aryl-6-[(2ꢁꢁ,3ꢁꢁ,4ꢁꢁ,6ꢁꢁ-tetra-O-
acetyl-β-D-glucopyranosyl)methyl]pyridine 3e/3k (1 mmol) in MeOH at 25◦C
was added a solution of NaOMe (10 mL, 10 mol%). The reaction mixture was
stirred till the disappearance of the starting material (TLC). After completion
of reaction, the reaction mixture was neutralized by 2% aq. HCl solution at
0◦C and filtered, and the filtrate was concentrated in vacuum to give a resid-
ual mass, which was triturated with a mixture of chloroform:methanol and
filtered. The filtrate was evaporated and the residue, so obtained, was dis-
solved in methanol and filtered through a short column of silica gel to afford
the products (4e) and (4k), respectively. The compounds were recrystallized
with methanol.
2-Amino-3-cyano-4-(4ꢁ-bromophenyl)-6-[(β-D-glucopyranosyl)methyl]pyridine
(4e)
It was obtained as white solid in 58% yield; m.p. 253–257◦C; Rf 0.5 (2:8,
MeOH:CHCl3); [α]2D5 −38.60 (c 0.1, MeOH, at 25◦C); IR (KBr) νmax cm−1: 3334
(OH stretching), 2208 (C N stretching), 1654, 1571, 1079; 1H NMR (300 MHz,
DMSO-d6) δ = 7.90 (d, 1H, J = 3.03 Hz, ArH), 7.61 (d, 1H, J = 4.62 Hz,
ArH), 7.21–7.17 (m, 1H, ArH), 6.86 (s, 1H, ArH), 3.06–2.80 (m, 6H), 2.51–2.43
(m, 1H); 13C NMR (50 MHz, DMSO-d6) δ = 164.3, 161.0, 152.7, 136.5, 132.1,
130.8, 123.5, 113.1, 85.5, 81.0, 78.8, 78.5, 74.3, 70.9, 61.7; Anal calcd for
C19H20BrN3O5: C, 50.68; H, 4.48; N, 9.33 found: C, 50.73; H, 4.49; N, 9.38;
ESMS m/z = 450 (M+H)+.
2-Amino-3-cyano-4-(thio-2-nyl)-6-[(β-D-glucopyranosyl)methyl]pyridine (4k)
It was obtained as gray solid in 52% yield; m.p. 235–238◦C; Rf 0.5 (2:8,
MeOH:CHCl3); [α]2D5 −46.31 (c 0.1, MeOH, at 25◦C); IR (KBr) νmax cm−1: 3407

Highly Functionalized Pyridylmethyl-C-β-D-Glycosides
143
(OH stretching), 2206 (C N stretching), 1655, 1579, 1092; 1H NMR (300 MHz,
DMSO-d6) δ = 7.59 (d, 2H, J = 8.546 Hz, ArH), 7.43 (d, 2H, J = 8.46 Hz,
ArH), 6.69 (s, 1H, ArH), 6.54 (s, 2H, NH2), 3.71–3.55 (m, 7H), 3.33–3.31 (m,
2H), 3.17–3.14 (m, 3H), 2.75–2.68 (m, 7H), 13C NMR (50 MHz, DMSO-d6) δ =
167.7, 165.5, 150.6, 143.0, 133.9, 133.6, 133.1, 122.2, 117.0, 84.9, 78.6, 75.5,
66.6, 64.8; Anal calcd for C17H19N3O5S: C, 54.10; H, 5.07; N, 11.13 found: C,
54.15; H, 5.12; N, 11.09; ESMS m/z = 378 (M+H)+.
General Procedure for the Preparation of 2-Amino-3-cyano-4-
aryl-6-[(2ꢀꢀ,3ꢀꢀ,6ꢀꢀ,2ꢀꢀꢀ,3ꢀꢀꢀ,4ꢀꢀꢀ,6ꢀꢀꢀ-hepta-O-acetyl-β-cellobiosyl)
methyl]pyridine (6a, 6b)
To a stirring solution of one of the selected benzylidenemalanonitriles (2a
and 2h) (1.0 mmol) and 3-(β-D-cellobiosyl)-propanone (5) (1.0 mmol) in toluene
(10 mL) was added ammonium acetate (1.5 mmol). Reaction mixture was re-
fluxed till the disappearance of (5) (TLC). Now, the reaction mixture was evap-
orated under reduced pressure. The residue was extracted with EtOAc/water
and the organic layer was dried (Na2SO4) and concentrated under reduced
pressure to give a crude mass. The latter was purified by column chromatog-
raphy on silica gel (60–120 mesh) using EtOAc:hexane as eluent to give cor-
responding 2-amino-4-aryl-3-cyano-pyridylmethylidene-β-C-peracetylated cel-
lobioside (6a and 6b).
2-Amino-3-cyano-4-(2ꢁ-napthyl)-6-[(2ꢁꢁ,3ꢁꢁ,6ꢁꢁ,2ꢁꢁꢁ,3ꢁꢁꢁ,4ꢁꢁꢁ,6ꢁꢁꢁ-hepta-O-acetyl-β-
cellobiosyl)methyl]pyridine (6a)
It was obtained as white solid in 39% yield; m.p. 150–153◦C; Rf 0.5 (4:98,
MeOH:CHCl3); [α]D25 −128.50 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 3452,
1
2245 (C N stretching), 1749 (O C O stretching), 1220; H NMR (300 MHz,
CDCl3) δ = 8.09 (s, 1H, ArH), 7.93–7.86 (m, 4H, ArH), 7.55–7.52 (m, 2H, ArH),
6.73 (s, 1H, ArH), 5.39 (s, 2H, NH2), 5.20–5.04 (5H), 4.91–4.86 (2H), 4.38–4.35
(1H), 4.17–3.87 (3H), 3.73–3.66 (3H), 2.45–2.41 (m, 2H), 2.08–1.97 (21H, 7 ×
COCH3); 13C NMR (50 MHz, CDCl3): δ = 170.4, 170.2, 170.0, 169.7, 169.2,
168.1, 160.8, 160.1, 133.7, 133.0, 128.8, 128.6, 128.1, 126.2, 125.2, 115.0, 100.6,
96.1, 95.5, 75.1, 74.0, 73.7, 72.9, 71.9, 71.5, 67.7, 61.7, 30.9, 20.6, 20.5; Anal
calcd for C43H47N3O7: C, 58.83; H, 5.40; N, 4.79; found: C, 58.87; H, 5.44; N,
4.72; ESMS m/z 878 (M+H)+
.
2-Amino-3-cyano-4-(4ꢁ-benzeloxyphenyl)-6-[(2ꢁꢁ,3ꢁꢁ,6ꢁꢁ,2ꢁꢁꢁ,3ꢁꢁꢁ,4ꢁꢁꢁ,6ꢁꢁꢁ-hepta-O-
acetyl-β-cellobiosyl)methyl]pyridine (6h)
It was obtained as white solid in 36% yield; m.p. 158–161◦C; Rf 0.5 (4:98,
MeOH:CHCl3); [α]D25 −133.30 (c 0.1, CHCl3, at 25◦C); IR (KBr) νmax cm−1: 3471,
1
2213 (C N stretching), 1752 (O C O stretching), 1235; H NMR (300 MHz,
CDCl3) δ = 7.58 (d, 2H, J = 8.55 Hz, ArH), 7.45–7.36 (m, 5H, ArH), 7.58

V. P. Pandey et al.
144
(d, 2H, J = 8.58 Hz, ArH), 6.62 (s, 1H, ArH), 5.24 (s, 2H, NH2), 5.21–5.04 (7H),
4.96–4.82 (2H), 4.51–4.35 (1H), 4.12–4.03 (3H), 3.75–3.55 (3H), 2.83–2.2.76
(m, 2H), 2.17–2.02 (21H, 7 × COCH3); 13C NMR (50 MHz, CDCl3) δ = 170.4,
170.1, 169.8, 169.2, 168.1, 160.8, 160.1, 133.7, 133.0, 129.6, 128.6, 128.1, 127.4,
115.2, 96.1, 95.5, 74.0, 72.9, 71.9, 67.8, 62.0, 61.6, 40.5, 20.5; Anal calcd for
C46H51N3O8: C, 59.16; H, 5.50; N, 4.50; found: C, 5920; H, 5.56; N, 4.45; ESMS
m/z 934 (M+H)+.
ACKNOWLEDGEMENTS
This is CDRI communication no. 8061. V.P.P. thanks CSIR, New Delhi, for the
award of SRF. We sincerely acknowledge the financial assistance from CSIR,
New Delhi and DRDO, New Delhi. SAIF CDRI is also acknowledged for pro-
viding spectroscopic data of the compounds.
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