Diastereoselective synthesis of galactopyranosyl amino esters and their transformation into C-nucleosides

Article abstract of DOI:10.1081/CAR-120030140

Galactopyranosylated olefinic ester (4) on conjugate addition of amines yielded stereoselectively galactopyranosylated amino esters (5-18) in fair to good yield. The selected amino esters (5, 6, 13, and 15-17) on reaction with isocyanates resulted in urei

Full text of DOI:10.1081/CAR-120030140

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Diastereoselective Synthesis of Galactopyranosyl
Amino Esters and Their Transformation into
C‐Nucleosides
Diksha Katiyar a , Ram Chandra Mishra a & Rama Pati Tripathi a
a Division of Medicinal Chemistry, Central Drug Research Institute, Lucknow, 226001,
India
Version of record first published: 18 Aug 2006.
To cite this article: Diksha Katiyar, Ram Chandra Mishra & Rama Pati Tripathi (2004): Diastereoselective Synthesis of
Galactopyranosyl Amino Esters and Their Transformation into C‐Nucleosides, Journal of Carbohydrate Chemistry, 23:1,
49-70
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JOURNAL OF CARBOHYDRATE CHEMISTRY
Vol. 23, No. 1, pp. 49–70, 2004
Diastereoselective Synthesis of Galactopyranosyl
Amino Esters and Their Transformation
into C-Nucleosides
*
Diksha Katiyar, Ram Chandra Mishra, and Rama Pati Tripathi
Division of Medicinal Chemistry, Central Drug Research Institute, Lucknow, India
ABSTRACT
Galactopyranosylated olefinic ester (4) on conjugate addition of amines yielded
stereoselectively galactopyranosylated amino esters (5–18) in fair to good yield. The
selected amino esters (5, 6, 13, and 15–17) on reaction with isocyanates resulted in
ureido galactopyranosyl amino esters (19–24) in very good yields. Lactamization of
˚
compounds 19–24 with DBU, 4 A MS, and tetrabutylammonium bromide in refluxing
toluene gave respective C-galactopyranosyl dihydropyrimidine-2,4-diones (25–30) in
respectable yields.
Key Words: Amino esters; Diastereoselection; Nucleosides; Galactopyranose.
INTRODUCTION
Sugar amino acids one of the important construction elements in nature and important
constituent of naturally occurring nucleoside antibiotics serve as versatile synthons in
organic synthesis.[1,2] Due to structural importance and involvement in many biological
processes chemical synthesis of amino sugar derivatives has been a fertile area in bio-
organic chemistry.[2] Glycosylated amino acids having amino and carboxyl functionalities
*
Correspondence: Rama Pati Tripathi, Division of Medicinal Chemistry, Central Drug Research
Institute, Lucknow 226001, India; Fax: (0522) 2223405, 2223938; E-mail: rpt_56@yahoo.com.
49
DOI: 10.1081/CAR-120030140
0732-8303 (Print); 1532-2327 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Katiyar, Mishra, and Tripathi
either in rings or as appendages serve as very good scaffold for the combinatorial
synthesis, of the library of glycoconjugates and glycopeptides of biological importance
particularly as peptido mimics.[3,4]
We have very recently embarked upon a program to the synthesis of biologically
important compounds from glycosyl amino acids particularly for antitubercular,[5] anti-
parasitic,[6] and antidiabetic activities.[7] Because of the importance of galactose sugars
in M. tuberculosis[8,9] and presence of galactopyranosyl skeleton in destomic acid (1)[10]
and lincosamine (2),[11] the important constituents of the antibiotics, we were interested
in the synthesis of galactopyranosyl amino esters, which could be transformed into
C-nucleosides. Galactopyranosyl dialdoses have successfully been used for chain elonga-
tion to synthesize a variety of biologically significant compounds.[12,13] Different
approaches have been adopted for the synthesis of galactopyranosyl amino sugars from
time to time.[14] In general N-functionality has been introduced at C-5 or C-6 in furanoses
and pyranoses, respectively, utilizing corresponding dialdose and 2-aminothiazole
aldehydes.[15] Stereoselective introduction of N- or heteronucleophiles to the glycosylated
olefinic esters has recently also been reported by others[16] and our group.[6] However,
reports on stereoselective synthesis of galactopyranosyl amino sugars by asymmetric
induction in Michael type reactions are very scanty.[17] The present work describes
the synthesis of the b-galactopyranosyl amino esters and their conversion into
C-nucleosides.
RESULTS AND DISCUSSION
Synthetic strategy (Schs. 1 and 2) begins with 1,2 : 3,4-di-O-isopropylidene-
a-D-galactopyranose which on oxidation with pyridinium chlorochromate in presence
˚
of 4 A MS yielded 1,2 : 3,4-di-O-isopropylidene-a-D-galacto-hexodialdo-1,5-pyranose 3
in 80% yield. Dialdose 3 on lithium hydroxide catalyzed olefination with triethyl
phosphonoacetate resulted in (E)-ethyl 6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-a-D-
galacto-6-eno-octopyranuronate 4 exclusively in quantitative yield. The structure and
geometry of the olefinic ester 4 was decided on the basis of 1H NMR spectral data where
the coupling constant (J6,7 ¼ 15.6 Hz) of vinylic protons H-6 and H-7 confirmed a trans
(E) relationship between the two protons.
Conjugate addition of ethanolic ammonia to the olefinic ester 4 led to the formation of
1
two diastereoisomers in 52 : 48 ratios. The ratio of isomers was determined by H NMR
spectrum of crude reaction mixture where H-1 appeared as “d” with different chemical
shifts in the two isomers. The conversion into amino esters was more than 90% at 258C.
The two isomers (5 and 5a) were separated by flash column chromatography over silica gel

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Galactopyranosyl Amino Esters
51
Scheme 1. Synthesis of galactopyranosyl amino esters.
and the structures were elucidated on the basis of spectral data. MS spectrum of the above
compounds showed [M þ H]þ at 346 while in 1H NMR spectrum H-1 appeared as “d” at
d 5.56 and d 5.51 in compounds 5 and 5a, respectively. Two “dd” signals at d 4.31 and at
around d 4.60 accounted for H-2 and H-3, respectively, in both the isomers. H-5 adjacent
to the newly generated stereogenic center C-6 appeared as “dd” at d 3.63 and 3.55 in
compounds 5 and 5a, respectively, while the proton attached to C-6 appeared as “m” at
around d 3.40 in 5 and as “ddd” at d 3.36 in compound 5a. The methylene protons at C-7
appeared as two “dd” at d 2.67 and 2.46 in 5 and at d 2.84 and 2.36 in compound 5a besides
other usual signals.
Similarly, conjugate addition of different amines including butylamine, heptyl-
amine, octylamine, dodecylamine, hexadecylamine and oleylamine, pyrrolidine, and

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Katiyar, Mishra, and Tripathi
Scheme 2. Synthesis of galactopyranosyl C-nucleosides.
piperidine, cyclopropyl amine and cyclohexyl amine and benzyl amine to the above
olefinic ester 4 was carried out successfully to give a diastereomeric mixture of
galactopyranosylated amino esters (Table 1). As evident from the table diastereoselec-
tion varies with the nature of amines used. Conjugate addition of ammonia resulted in
almost no diastereoselection (52 : 48). With alkyl-substituted amines including
n-butylamine (60 : 40) and long chain alkyl substituted amines a low diastereoselection
was observed. A considerable diastereoselection was observed with benzylamine
(84 : 16), pyrrolidine (93 : 07), and piperidine (95 : 05). However, with piperidine as
nucleophile reaction was very slow and a longer reaction time resulted in glycosylated
amino acid (9b) along with the amino esters (9 and 9a). Different reaction conditions
for better diastereoselection, including lowering of temperature and change in solvents
resulted in no improvement in diastereoselectivity. In most of the cases the minor
diastereoisomers (6a, 7a, 8a, 9a, 10a, 13a, and 15a) formed could not be separated
even by repeated column chromatography and were found to be contaminated with
starting olefinic ester. However, minor isomers 5a, 14a, and 16a formed in their
respective reactions were separated by flash column chromatography in pure form.
Compounds 11a and 12a could only be separated in minor amount for the purpose of
NMR spectroscopy by repeated column chromatography over SiO2. Galactopyranosy-
lated amino esters 17 and 18 were obtained by reductive arylation of compound 5,

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Galactopyranosyl Amino Esters
53
Table 1. Galactopyranosylated amino esters synthesized either by conjugate addition of amines to
the olefinic ester 4 (5–16) or by reductive amination (17 and 18).
Ratio of
isomers
S : R
Time
(hr)
Yield
(%)
Compound
R1R2N
5, 5a
6, 6a
7, 7a
NH2
24
16
18
52 : 48
85 : 15
60 : 40
90a
82b
79b
CH3(CH2)3NH
8, 8a
16
24
22
93 : 07
95 : 05
62 : 38
70b
65b
90b
9, 9a
10, 10a
11, 11a
12, 12a
13, 13a
14, 14a
15, 15a
16, 16a
17
CH3(CH2)6NH
CH3(CH2)7NH
24
18
14
18
16
16
16
16
53 : 47
67 : 33
70 : 30
64 : 36
75 : 25
84 : 16
—
80b
84b
90b
88a
82b
86a
80a
70a
CH3(CH2)11NH
CH3(CH2)15NH
CH3(CH2)8CH55CH(CH2)7CH3
C6H5CH2NH
C6H3(OCH3)2CH2NH
C6H4(OH)CH2NH
18
—
aIsolated yields.
1
bYields calculated on the basis of integration of H NMR signal (H-1).
whereas compound 16 could be obtained by both the methods. Thus, reaction of
compound 5 with benzaldehyde, 3,4-dimethoxy benzaldehyde and 2-hydroxy benzal-
dehyde separately in the presence of trimethyl orthoformate followed by reduction of
the intermediates with sodium cyanoborohydride afforded galactopyranosyl aryl amino
esters 16, 17, and 18, respectively, in fair to good yield.
Next we aimed at the synthetic utility of galactopyranosylated amino esters in the
preparation of C-nucleoside analogs. Few of the amino esters were selected keeping in
mind the structural diversity. Thus, the galactopyranosyl amino ester (5) on reaction with
4-chlorophenyl isocyanate gave ureido galactopyranosyluronate (19) in 69% yield. Similar
reaction of compounds (6, 13, 15–17) with benzyl or 4-chlorophenyl isocyanates resulted
in ureido galactopyranosyl amino esters 20–24 (Sch. 2, Table 2) in very good yields.
The structural assignments of the above compounds were based on spectroscopic
data and analysis. Absorption bands in the IR spectrum of 19 at 3341 (NH stretch),
1657 (CONH I band) and 1545 (CONH II band) indicated the formation of urea
1
derivative. In H NMR spectrum, four aromatic protons appeared as “m” at around
d 7.24 and a “d” at d 5.44 accounted for –NHCO. H-1, H-2, H-3, and H-4 appeared as
“dd” at d 5.56, 4.32, 4.60, and 4.25, respectively. While H-5, –OCH2, and H-6
1
appeared as “m” at around d 4.10 besides other usual H NMR signals. The formation
of urea derivative was further substantiated by 13C NMR spectrum where a signal at
d 155.8 showed a –CONH group besides other usual signals. The urea derivatives, so

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Katiyar, Mishra, and Tripathi
Table 2. Galactopyranosylated ureidyl derivatives 19–24 and C-nucleosides 25–30.
Reaction
time (hr)
Compound
R
R0
Yield (%)
19
20
21
22
23
24
25
26
27
28
29
30
H
4-Cl-phenyl
Benzyl
Benzyl
7.0
4.0
4.0
4.0
4.0
3.0
2.0
6.0
4.0
4.0
4.5
3.5
69
95
95
95
98
98
70
75
89
90
92
95
Cyclopropyl
Dodecyl
Oleyl
4-Cl-phenyl
4-Cl-phenyl
Benzyl
Benzyl
3,4-Dimethoxyphenylmethyl
H
Cyclopropyl
4-Cl-phenyl
Benzyl
Benzyl
Dodecyl
Oleyl
4-Cl-phenyl
4-Cl-phenyl
Benzyl
Benzyl
3,4-Dimethoxyphenylmethyl
obtained, on reaction with our recently discovered lactamization reagent[18] (DBU, 4 A
molecular sieve and tetrabutyl ammonium bromide) in refluxing toluene gave corres-
ponding nucleosides 25–30 (Sch. 2, Table 2) in fair to good yields. The structures of
˚
1
the nucleosides were determined on the basis of spectroscopic data and analysis. In H
NMR spectrum absence of signals corresponding to –OCH2CH3 at around d 4.10 and
1.20, respectively, was indication for cyclization. H-6 was shifted to downfield and
appeared as “m” at around d 4.06–3.62, while in 13C NMR appearance of two signals
at around d 165 (–NCON–) and d 152 (–CON–) besides other usual signals confirm
the structure.
The stereochemistry at C-6 in galactopyranosyl amino esters obtained by conjugate
addition of amines to the galactopyranosyl olefinic esters has tentatively been predicted
on the basis of literature precedent and mechanistic grounds. It is documented that
conjugate addition of nucleophiles to galactopyranosylated olefins gives two epimers
the major one “S” while the minor isomer has “R” stereochemistry at C-6.[19] The
above stereochemistry at C-6 has been rationalized based on transition state models and
the extent of approach of the nucleophile to the prochiral center. Looking into the
transition state models A (Cram) and B (Felkin-Anh), the major attack of nucleophilic
amines to C-6 in olefin would take place from the side of the least bulky group
(hydrogen attached to C-5 of the pyranose ring, the “si” diastereoface), and hence the
major reaction product has “S” configuration at C-6 while that of the minor one is “R”
(Fig. 1). This “S” configuration is maintained in ureidyl derivatives as well as in
cyclization products as no inversion is taking place during the course of these reactions.
The threo relationship between protons at C-50 and at C-6 in nucleosides has been
1
substantiated by H NMR spectrum of a prototype dihydropyrimidin-2,4-dione (29),
0
where J5 ,6 was found to be 9.0 Hz indicating a dihedral angle of either about 08 or
1808. To confirm the spatial relationship between H-50 and H-6 in compound 29 NOE
experiment was done which did not show any interaction between H-50 (d 4.05) and
H-6 (at around d 3.86) confirming trans relationship between these two protons and
hence the compound has “S” configuration at C-6.

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Galactopyranosyl Amino Esters
55
Figure 1. Transition state models for the reaction.
EXPERIMENTAL
General Methods
Thin-layer chromatography was carried out on silica gel (Kiesel 60-F254, Merck,
Darmstadt, Germany) and spots were developed in iodine vapors and also by spraying with
5% sulfuric acid in alcohol followed by heating at 1008C. Column chromatography was
carried out on flash silica gel (230–400 mesh, Merck) using the indicated eluent. IR
spectra were recorded as thin films on KBr plates with a Perkin Elmer 881
spectrophotometer (Beaconsfield, Buckinghamshire, England). NMR spectra were
recorded on Bruker spectrometers 200 and 300 MHz (Fallanden, Switzerland) and
reference used was CDCl3. Chemical shifts were given as d ppm values and “J” values
were given in Hertz (Hz). Elemental analyses were performed on a Perkin–Elmer 2400 II
elemental analyzer (Rodano, Milan, Italy). The optical rotations were measured in a
1.0 dm tube with Jasco dip-140 polarimeter (Rudolph Research, Flanders, NJ, USA) in
chloroform, methanol, or ethyl acetate. The excess of the reagents or solvents were
evaporated under reduced pressure at a bath temperature between the ranges 55–608C.
1,2 : 3,4-Di-O-isopropylidene-a-D-galacto-hexodialdo-1,5-pyranose (3)
˚
To a magnetically stirred slurry of anhydrous 4 A molecular sieve (10.0 g) and
pyridinium chlorochromate (20.5 g, 96.2 mmol) in dry CH2Cl2 (250 mL), solution of
1,2 : 3,4-di-O-isopropylidene-a-D-galactopyranose (10.0 g, 38.76 mmol) in dry CH2Cl2
(50 mL) was added and stirred for 2 hr. Reaction mixture filtered using Celite pad, solid
cake washed with more CH2Cl2 and evaporated under reduced pressure to give a crude
product. It was purified by column chromatography over SiO2 using hexane : ethyl acetate
(7 : 3) as eluent to give 3[20] as colorless oil. Yield: 5.6 g (56.4%), Rf 0.5 (hexane : ethyl
acetate, 3 : 2); [a]2D0 257.68 (c 0.187, chloroform); MS (FAB) ¼ m/z 259 (M þ H)þ; IR
1
(Neat) nmax cm21: 1741, 1614; H NMR (200 MHz, CDCl3): d 9.62 (s, 1H, CHO), 5.67
(d, J ¼ 4.8 Hz, 1H, H-1), 4.65 (dd, J ¼ 7.8 and 2.1 Hz, 1H, H-3), 4.60 (dd, J ¼ 7.8 and

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Katiyar, Mishra, and Tripathi
1.7 Hz, 1H, H-4), 4.38 (dd, J ¼ 4.8 and 2.1 Hz, 1H, H-2), 4.19 (d, J ¼ 1.7 Hz, 1H, H-5),
1.51, 1.44, 1.35, 1.32 [each s, each 3H, 2 ꢀ C(CH3)2]; 13C NMR (50 MHz, CDCl3):
d 200.5, 110.4, 109.4, 96.6, 73.6, 72.1, 70.9, 68.3, 26.4, 26.2, 25.2.
(E)-Ethyl 6,7-Dideoxy-1,2 : 3,4-di-O-isopropylidene-a-D-galacto-
6-eno-octopyranuronate (4)
The solution of compound 3 (2 g, 7.75 mmol) in anhydrous THF (15 mL) and triethyl
phosphono acetate (1.53 mL, 7.75 mmol) was magnetically stirred at 258C. To the stirring
.
reaction mixture LiOH H2O (0.33 g, 7.75 mmol) was added and stirring continued for
10 hr. The solvent evaporated under reduced pressure to give a residual mass. The latter
was dissolved in dichloromethane (50 mL) and washed with water (2 ꢀ 10 mL). The
organic layer was dried (Na2SO4) and evaporated under reduced pressure to give a crude
mass, which was chromatographed over SiO2 using hexane : ethyl acetate (4 : 1) as eluent
to give 4 as colorless oil. Yield: 2.16 g (85%); Rf 0.6 (hexane : ethyl acetate, 3 : 2); [a]D20
245.58 (c 0.2, chloroform); MS (FAB): m/z ¼ 329 (M þ H)þ; IR (Neat) nmax cm21
:
1720; 1H NMR (200 MHz, CDCl3): d 6.88 (dd, J ¼ 15.7 and 4.4 Hz, 1H, H-6), 6.13 (dd,
J ¼ 15.7 Hz, 1H, H-7), 5.59 (d, J ¼ 5.0 Hz, 1H, H-1), 4.63 (dd, J ¼ 7.7 and 2.3 Hz, 1H,
H-3), 4.45 (dd, J ¼ 4.4 and 2.0 Hz, 1H, H-5), 4.35 (dd, J ¼ 5.0 and 2.3 Hz, 1H, H-2), 4.29
(dd, J ¼ 7.7 and 2.0 Hz, 1H, H-4), 4.16 (q, J ¼ 7.1 Hz, 2H, –OCH2), 1.51, 1.43, 1.34, 1.32
[each s, each 3H, 2 ꢀ C(CH3)2], 1.26 (t, J ¼ 7.1 Hz, 3H, –OCH2CH3); 13C NMR
(50 MHz, CDCl3): d 163.0, 146.6, 120.6, 109.7, 109.3, 96.8, 74.5, 71.4, 70.6, 65.9, 60.7,
26.8, 25.5, 24.8, 14.6.
Anal. Calcd for C16H24O7: C, 58.53; H, 7.31. Found: C, 58.52; H, 7.30.
Ethyl 6-Amino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-b-L-glycero-
a-D-galacto-octopyranuronate (5)
A solution of compound 4 (3.0 g, 9.1 mmol) in ethanolic ammonia (30 mL) was
magnetically stirred at 308C for 24 hr. Solvent evaporated and the residue was chroma-
tographed over SiO2 column using chloroform : methanol (9 : 1) as eluent to give
compound 5 as colorless oil. Rf 0.43 (chloroform : methanol, 9 : 1); MS (FAB) ¼ m/z 346
(M þ H)þ; [a]2D0 265.18 (c 0.18, chloroform); IR (Neat) nmax cm21: 3387, 1727; 1H NMR
(200 MHz, CDCl3): d 5.56 (d, J ¼ 5.0 Hz, 1H, H-1), 4.60 (dd, J ¼ 8.1 and 2.2 Hz, 1H,
H-3), 4.44 (dd, J ¼ 8.1 and 1.7 Hz, 1H, H-4), 4.31 (dd, J ¼ 5.0 and 2.2 Hz, 1H, H-2), 4.14
(q, J ¼ 7.1 Hz, 2H, –OCH2), 3.63 (dd, J ¼ 6.9 and 1.7 Hz, 1H, H-5), 3.43–3.35 (m, 1H,
H-6), 2.67 and 2.46 (each dd, J ¼ 16.4 and 5.0 Hz, 2H, H-7A and H-7B), 1.67 (bs, 2H,
NH2), 1.51, 1.44, 1.35 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.25 (t, J ¼ 7.2 Hz, 3H,
–OCH2CH3); 13C NMR (CDCl3): d 172.4, 109.7, 109.0, 96.9, 72.0, 71.3, 71.1, 70.7, 60.8,
48.9, 38.1, 26.3, 25.3, 24.8, 24.7, 14.57.
Anal. Calcd for C16H27NO7: C, 55.65; H, 7.82; N, 4.05. Found: C, 55.67; H, 7.88;
N, 4.05.

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Galactopyranosyl Amino Esters
57
Ethyl 6-Amino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-a-D-glycero-D-
galacto-octopyranuronate (5a)
Rf 0.54 (chloroform : methanol, 9 : 1); MS (FAB) ¼ m/z 346 (M þ H)þ; [a]D20 264.48
1
(c 0.22, chloroform); IR (Neat) nmax cm21: 3429, 1654; H NMR (200 MHz, CDCl3): d
5.51 (d, J ¼ 5.0 Hz, 1H, H-1), 4.62 (dd, J ¼ 7.9 and 2.4 Hz, 1H, H-3), 4.44 (dd, J ¼ 7.9
and 1.8 Hz, 1H, H-4), 4.31 (dd, J ¼ 5.0 and 2.4 Hz, 1H, H-2), 4.10 (q, J ¼ 7.1 Hz, 2H,
–OCH2), 3.55 (dd, J ¼ 8.8 and 1.8 Hz, 1H, H-5), 3.36 (ddd, J ¼ 8.8, 8.5, and 3.2 Hz, 1H,
H-6), 2.84 (dd, J ¼ 16.4 and 3.2 Hz, 1H, H-7A), 2.36 (dd, J ¼ 16.4 and 8.5 Hz, 1H, H-7B),
1.67 (bs, 2H, NH2), 1.51, 1.44, 1.35 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.25
(t, J ¼ 7.2 Hz, 3H, –OCH2CH3); 13C NMR (CDCl3): d 173.0, 109.6, 108.9, 96.8, 71.1,
70.9, 70.7, 69.2, 60.6, 48.7, 38.9, 26.3, 25.3, 24.9, 24.6, 14.6.
Anal. Calcd for C16H27NO7: C, 55.65; H, 7.82; N, 4.05. Found: C, 55.60; H, 7.90;
N, 3.89.
Ethyl 6-Cyclopropylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-a-D-galacto-octopyranuronate (6)
A solution of compound 4 (3 g, 9.1 mmol) and cyclopropyl amine (0.63 mL,
9.1 mmol) in alcohol (30 mL) was magnetically stirred at 308C for 16 hr. Solvent
evaporated and the residue was chromatographed over SiO2 column using hexane : ethyl
acetate (4 : 1) as eluent to give title compound. Colorless solid, mp 70–728C; Rf 0.51
(hexane : ethyl acetate, 4 : 1); [a]2D0 243.38 (c 0.15, chloroform); MS (FAB) ¼ m/z 386
1
(M þ H)þ; IR (Neat) nmax cm21: 3371, 1727; H NMR (200 MHz, CDCl3): d 5.56
(d, J ¼ 5.0 Hz, 1H, H-1), 4.59 (dd, J ¼ 8.0 and 2.0 Hz, 1H, H-3), 4.37 (d, J ¼ 8.0 Hz, 1H,
H-4), 4.33 (dd, J ¼ 5.0 and 2.0 Hz, 1H, H-2), 4.12 (q, J ¼ 7.1 Hz, 2H, –OCH2), 3.94
(d, J ¼ 7.3 Hz, 1H, H-5), 3.41–3.31 (m, 1H, H-6), 2.75 and 2.62 (each dd, 2H, J ¼ 15.7
and 5.4 Hz, H-7A and H-7B), 2.14 (m, 2H, NH and NCH), 1.51, 1.45, 1.32 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.25 (t, J ¼ 7.1 Hz, OCH2CH3), 0.44–0.38 (m, 4H, cyclopropyl ring
protons); 13C NMR (CDCl3): d 172.7, 109.5, 108.9, 97.1, 72.0, 71.5, 71.0, 68.6, 60.6, 56.6,
36.0, 29.0, 26.4, 25.3, 24.7, 14.5, 7.5, 5.8.
Anal. Calcd for C19H31NO7: C, 59.22; H, 8.05; N, 3.63. Found: C, 59.25; H, 8.11;
N, 3.63.
Ethyl 6-Butylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (7)
Colorless oil; Rf 0.56 (hexane : ethyl acetate, 3 : 2); [a]2D0 260.08 (c 0.15, chloroform);
MS (FAB) ¼ m/z 402 (M þ H)þ; IR (Neat) nmax cm21: 3344, 1733; 1H NMR (200 MHz,
CDCl3): d 5.55 (d, J ¼ 5.0 Hz, 1H, H-1), 4.59 (dd, J ¼ 7.9 and 2.3 Hz, 1H, H-3), 4.36 (dd,
J ¼ 7.9 and 1.5 Hz, 1H, H-4), 4.31 (dd, J ¼ 5.0 and 2.3 Hz, 1H, H-2), 4.12 (q, J ¼ 7.1 Hz,
2H, –OCH2), 3.86 (dd, J ¼ 7.1 and 1.5 Hz, 1H, H-5), 3.27–3.18 (m, 1H, H-6), 2.72–2.45
(m, 4H, NHCH2 and H-7), 1.76 (bs, 1H, NH), 1.51, 1.45, 1.32 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.29–1.22 (m, 7H, 2 ꢀ CH2 and –OCH2CH3), 0.89 (t, J ¼ 7.2 Hz,

ORDER
REPRINTS
58
Katiyar, Mishra, and Tripathi
3H, –CH2CH3); 13C NMR (CDCl3): d 172.7, 109.6, 108.9, 97.0, 72.0, 71.5, 71.0, 68.8,
60.6, 56.0, 47.0, 35.8, 32.6, 26.3, 25.3, 24.7, 20.8, 14.5, 14.4.
Anal. Calcd for C20H35NO7: C, 59.85; H, 8.72; N, 3.49. Found: C, 60.02; H, 9.07;
N, 3.46.
Ethyl 6-(Pyrrolidin-1-yl)-6,7-Dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (8)
Colorless oil; Rf 0.58 (hexane : ethyl acetate, 3 : 2); [a]2D0 2110.68 (c 0.15,
chloroform), MS (FAB) ¼ m/z 400 (M þ H)þ; IR (Neat) nmax cm21: 2986, 2930, 1721;
1H NMR (200 MHz, CDCl3): d 5.56 (d, J ¼ 5.0 Hz, 1H, H-1), 4.57 (dd, J ¼ 8.0 and
2.2 Hz, 1H, H-3), 4.32 (d, J ¼ 8.0 Hz, 1H, H-4), 4.26 (dd, J ¼ 5.0 and 2.2 Hz, 1H, H-2),
4.12 (q, J ¼ 7.2 Hz, 2H, –OCH2), 3.77–3.67 (m, 2H, H-5 and H-6), 2.73–2.40 (m, 6H,
2 ꢀ NCH2 and H-7), 1.68 (m, 4H, pyrrolidine protons), 1.58, 1.51, 1.43, 1.32 [each s, each
3H, 2 ꢀ C(CH3)2], 1.23 (t, J ¼ 7.1 Hz, –OCH2CH3); 13C NMR (CDCl3): d 173.1, 109.2,
108.6, 96.1, 72.2, 71.2, 70.6, 67.6, 60.5, 55.4, 50.2, 36.5, 26.2, 25.6, 24.7, 23.2, 14.5.
Anal. Calcd for C20H33NO7: C, 60.15; H, 8.27; N, 3.50. Found: C, 60.21; H, 8.27;
N, 3.22.
Ethyl 6-(Piperidin-1-yl)-6,7-Dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (9)
Colorless oil; Rf 0.54 (hexane : ethyl acetate, 3 : 2); [a]2D0 2108.48 (c 0.113, chloro-
1
form); MS (FAB) ¼ m/z 414 (M þ H)þ; IR (Neat) nmax cm21: 2987, 2932, 1721; H
NMR (200 MHz, CDCl3): d 5.57 (d, J ¼ 5.1 Hz, 1H, H-1), 4.64 (dd, J ¼ 7.7 and 2.1 Hz,
1H, H-3), 4.35 (dd, J ¼ 5.1 and 2.1 Hz, 1H, H-2), 4.29 (dd, J ¼ 7.7 and 1.4 Hz, 1H, H-4),
4.15 (q, J ¼ 7.0 Hz, 2H, –OCH2), 3.78 (d, J ¼ 8.7 Hz, H-5), 3.41–3.31 (m, 1H, H-6), 2.81
.
and 2.31 (m, 6H, H-7 and 2 ꢀ N CH2), 1.51, 1.51, 1.33 [each s, 3H, 3H, 6H,
2 ꢀ C(CH3)2], 1.32–1.24 (m, 9H, piperidine protons and –OCH2CH3); 13C NMR
(CDCl3): d 172, 109.2, 108.3, 96.5, 73.2, 71.7, 70.5, 68.1, 67.4, 61.4, 60.3, 50.4, 35.5, 27.1,
26.0, 25.9, 24.8, 24.1, 14.2.
Anal. Calcd for C21H35NO7: C, 61.01; H, 8.47; N, 3.39. Found: C, 60.92; H, 8.49;
N, 3.37.
Ethyl 6-(Piperidin-1-yl)-6,7-Dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronic acid (9b)
Yield: 30%, Colorless solid, mp 158–608C; Rf 0.45 (chloroform : methanol, 9 : 1);
[a]2D0 2101.48 (c 0.138, chloroform); MS (FAB) ¼ m/z 386 (M þ H)þ; IR (Neat) nmax
cm21: 3432, 1661; 1H NMR (200 MHz, CDCl3): d 5.55 (d, J ¼ 5.1 Hz, 1H, H-1), 4.61 (dd,
J ¼ 7.9 and 2.5 Hz, 1H, H-3), 4.35 (dd, J ¼ 5.1 and 2.5 Hz, 1H, H-2), 4.08 (d, J ¼ 7.9 and
.
1.5 Hz, 1H, H-4), 3.78 (dd, J ¼ 9.8 and 1.5 Hz, H-5), 3.40–2.94 (m, 5H, H-6, 2 ꢀ N CH2),
2.62 and 2.24 (each dd, J ¼ 13.0 and 4.1 Hz, 2H, H-7), 1.76 (m, 6H, piperidine protons),

ORDER
REPRINTS
Galactopyranosyl Amino Esters
59
1.51, 1.41, 1.34, 1.32 [each s, each 3H, 2 ꢀ C(CH3)2]; 13C NMR (CDCl3): d 173, 109.8,
108.8, 96.3, 70.7, 70.5, 70.0, 67.7, 61.5, 53.0, 29.7, 25.9, 25.8, 24.7, 24.3, 23.4.
Anal. Calcd for C19H31NO7: C, 59.22; H, 8.05; N, 3.63. Found: C, 58.98; H, 7.84;
N, 3.71.
Ethyl 6-Cyclohexylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (10)
Colorless oil; Rf 0.52 (hexane : ethyl acetate, 7 : 3); [a]2D0 272.28 (c 0.175,
chloroform); MS (FAB) ¼ m/z 428 (M þ H)þ; IR (Neat) nmax cm21: 3340, 1730;
1H NMR (200 MHz, CDCl3): d 5.55 (d, J ¼ 5.1 Hz, 1H, H-1), 4.56 (dd, J ¼ 7.9 and
2.1 Hz, 1H, H-3), 4.37 (dd, J ¼ 7.9 and 1.5 Hz, 1H, H-4), 4.28 (dd, J ¼ 5.0 and 2.1 Hz,
1H, H-2), 4.11 (q, J ¼ 7.1 Hz, 2H, –OCH2), 3.82 (dd, J ¼ 6.6 and 1.5 Hz, 1H, H-5), 3.40–
3.31 (m, 1H, H-6), 2.68 (dd, J ¼ 15.5 and 5.7 Hz, 1H, H-7A), 2.51–2.41 (m, 2H, NHCH
and H-7B), 1.88–1.67 (m, 5H, 2 ꢀ NCHCH2 and NH), 1.50, 1.45, 1.32 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.28–1.15 (m, 9H, cyclohexyl ring protons and –OCH2CH3);
13C NMR (CDCl3): d 172.6, 109.1, 108.4, 96.7, 71.6, 71.1, 70.7, 68.6, 60.1, 54.6, 53.0,
37.1, 34.4, 33.5, 25.9, 25.2, 24.9, 24.3, 14.2.
Anal. Calcd for C22H37NO7: C, 61.8; H, 8.66; N, 3.27. Found: C, 61.76; H, 8.67;
N, 3.22.
Ethyl 6-Heptylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (11)
Colorless oil; Rf 0.47 (hexane : ethyl acetate, 7 : 3); [a]2D0 242.28 (c 0.138,
chloroform); MS (FAB) ¼ m/z 444 (M þ H)þ; IR (Neat) nmax cm21: 3429, 1732;
1H NMR (200 MHz, CDCl3): d 5.55 (d, J ¼ 5.0 Hz, 1H, H-1), 4.59 (dd, J ¼ 8.0 and
2.2 Hz, 1H, H-3), 4.35 (dd, J ¼ 8.0 and 1.4 Hz, 1H, H-4), 4.30 (dd, J ¼ 5.0 and 2.2 Hz, 1H,
H-2), 4.12 (q, J ¼ 7.1 Hz, 2H, –OCH2), 3.86 (d, J ¼ 7.2 Hz, 1H, H-5), 3.27–3.18 (m, 1H,
H-6), 2.72–2.45 (m, 4H, NHCH2 and H-7), 1.85 (bs, 1H, NH), 1.51, 1.45, 1.32 [each s, 3H,
3H, 6H, 2 ꢀ C(CH3)2], 1.29–1.22 (m, 13H, 5 ꢀ CH2 and –OCH2CH3), 0.87
(t, J ¼ 6.6 Hz, 3H, –CH2CH3); 13C NMR (CDCl3): d 172.3, 109.2, 108.5, 96.6, 71.6,
71.1, 70.6, 68.4, 60.2, 55.6, 47.1, 35.6, 31.8, 30.2, 29.2, 27.3, 25.9, 24.9, 24.3, 22.6,
14.1, 14.0.
Anal. Calcd for C23H41NO7: C, 62.30; H, 9.25; N, 3.16. Found: C, 62.31; H, 9.25;
N, 3.16.
Ethyl 6-Heptylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
a-D-glycero-D-galacto-octopyranuronate (11a)
Colorless oil; Rf 0.65 (hexane : ethyl acetate, 7 : 3); [a]2D0 253.98 (c 0.375,
1
chloroform), MS (FAB) ¼ m/z 444 (M þ H)þ; IR (Neat) nmax cm21: 3346, 1725; H
NMR (200 MHz, CDCl3): d 5.49 (d, J ¼ 5.0 Hz, 1H, H-1), 4.57 (dd, J ¼ 7.9 and 2.1 Hz,
1H, H-3), 4.45 (dd, J ¼ 7.9 and 1.5 Hz, 1H, H-4), 4.26 (dd, J ¼ 5.0 and 2.1 Hz, 1H, H-2),

ORDER
REPRINTS
60
Katiyar, Mishra, and Tripathi
4.12 (q, J ¼ 7.1 Hz, 2H, –OCH2), 3.68 (d, J ¼ 8.4 Hz, 1H, H-5), 3.26–3.16 (m, 1H, H-6),
2.79 (dd, J ¼ 15.9 and 4.0 Hz, 1H, H-7A), 2.61 (t, J ¼ 6.8 Hz, 2H, NCH2), 2.45 (dd,
J ¼ 15.9 and 7.4 Hz, 1H, H-7B), 1.58 (s, 1H, NH), 1.49, 1.44, 1.33 [each s, 3H, 3H, 6H,
2 ꢀ C(CH3)2], 1.30–1.21 (m, 13H, 5 ꢀ CH2 and –OCH2CH3), 0.87 (t, J ¼ 6.7 Hz,
3H, –CH2CH3); 13C NMR (CDCl3): d 173.1, 109.3, 108.7, 96.9, 71.4, 71.0, 69.1, 67.8,
60.4, 54.5, 47.3, 35.6, 32.2, 30.8, 29.6, 27.6, 26.3, 25.3, 24.8, 22.9, 14.6, 14.4.
Anal. Calcd for C23H41NO7: C, 62.30; H, 9.25; N, 3.16. Found: C, 62.11; H, 8.93; N, 3.26.
Ethyl 6-Octylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (12)
Colorless oil; Rf 0.46 (hexane : ethyl acetate, 7 : 3); [a]2D0 243.48 (c 0.175,
1
chloroform); MS (FAB) ¼ m/z 458 (M þ H)þ; IR (Neat) nmax cm21: 3369, 1732; H
NMR (200 MHz, CDCl3): d 5.56 (d, J ¼ 5.0 Hz, 1H, H-1), 4.60 (dd, J ¼ 8.0 and 2.0 Hz,
1H, H-3), 4.36 (d, J ¼ 8.0 Hz, 1H, H-4), 4.30 (dd, J ¼ 5.0 and 2.0 Hz, 1H, H-2), 4.12
(q, J ¼ 7.1 Hz, 2H, –OCH2), 3.86 (d, J ¼ 7.1 Hz, 1H, H-5), 3.27–3.18 (m, 1H, H-6),
2.72–2.46 (m, 4H, NHCH2 and H-7), 1.95 (bs, 1H, NH), 1.51, 1.45, 1.32 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.29–1.22 (m, 15H, 6 ꢀ CH2 and –OCH2CH3), 0.87 (t, J ¼ 6.6 Hz,
3H, –CH2CH3); 13C NMR (CDCl3): d 172.7, 109.6, 108.9, 97.0, 72.0, 71.5, 71.0, 68.7,
60.6, 56.0, 47.5, 36.0, 32.2, 30.5, 29.8, 29.6, 27.7, 26.3, 25.3, 24.7, 23.0, 14.5, 14.4.
Anal. Calcd for C24H43NO7: C, 63.01; H, 9.40; N, 3.06. Found: C, 63.0; H, 9.32;
N, 2.89.
Ethyl 6-Octylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
a-D-glycero-D-galacto-octopyranuronate (12a)
Colorless oil; Rf 0.63 (hexane : ethyl acetate, 7 : 3); [a]2D0 256.78 (c 0.275,
chloroform); MS (FAB) ¼ m/z 458 (M þ H)þ; IR (Neat) nmax cm21: 3399, 1725;
1H NMR (200 MHz, CDCl3): d 5.50 (d, J ¼ 4.9 Hz, 1H, H-1), 4.60 (dd, J ¼ 7.7 and
2.0 Hz, 1H, H-3), 4.45 (d, J ¼ 7.7 Hz, 1H, H-4), 4.27 (dd, J ¼ 4.9 and 2.0 Hz, 1H, H-2),
4.12 (q, J ¼ 7.0 Hz, 2H, –OCH2), 3.68 (d, J ¼ 8.4 Hz, 1H, H-5), 3.26–3.17 (m, 1H, H-6),
2.79 (dd, J ¼ 16.0 and 4.0 Hz, 1H, H-7A), 2.61 (t, J ¼ 6.7 Hz, 2H, NCH2), 2.45
(dd, J ¼ 16.0 and 7.5 Hz, 1H, H-7B), 1.63 (bs, 1H, NH), 1.49, 1.44, 1.34 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.30–1.22 (m, 15H, 6 ꢀ CH2 and –OCH2CH3), 0.87 (t, J ¼ 6.6 Hz,
3H, 2CH2CH3); 13C NMR (CDCl3): d 173.2, 109.3, 108.7, 96.9, 71.4, 70.9, 69.1, 67.9,
60.5, 54.5, 47.3, 35.6, 32.2, 30.9, 29.9, 29.7, 27.7, 26.4, 25.3, 24.7, 23.0, 14.6, 14.4.
Anal. Calcd for C24H43NO7: C, 63.01; H, 9.40; N, 3.06. Found: C, 62.89; H, 9.40;
N, 3.10.
Ethyl 6-Dodecylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (13)
Colorless oil; Rf 0.45 (hexane : ethyl acetate, 4 : 1); [a]2D0 248.68 (c 0.175,
chloroform); MS (FAB) ¼ m/z 514 (M þ H)þ; IR (Neat) nmax cm21: 3340, 1730;

ORDER
REPRINTS
Galactopyranosyl Amino Esters
61
1H NMR (200 MHz, CDCl3): d 5.55 (d, J ¼ 5.1 Hz, 1H, H-1), 4.58 (dd, J ¼ 7.9 and
2.1 Hz, 1H, H-3), 4.35 (d, J ¼ 7.9 Hz, 1H, H-4), 4.30 (dd, J ¼ 5.1 and 2.1 Hz, 1H, H-2),
4.12 (q, J ¼ 7.1 Hz, 2H, –OCH2), 3.85 (d, J ¼ 7.1 Hz, 1H, H-5), 3.23–3.20 (m, 1H, H-6),
2.71–2.46 (m, 4H, NHCH2 and H-7), 2.09 (bs, 1H, NH), 1.51, 1.44, 1.32 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.25–1.21 (m, 23H, 10 ꢀ CH2 and –OCH2CH3), 0.88 (t, J ¼ 6.6 Hz,
3H, –CH2CH3); 13C NMR (CDCl3): d 172.7, 109.5, 108.9, 97.1, 72.0, 71.2, 71.1, 68.8,
60.6, 56.0, 47.5, 36.0, 35.6, 32.3, 30.9, 30.6, 30.0, 29.9, 29.8, 29.7, 27.7, 26.4, 25.3, 24.7,
23.0, 14.6, 14.4.
Anal. Calcd for C28H51NO7: C, 65.49, H, 9.94, N, 2.72. Found: C, 65.50, H, 10.01,
N, 2.74.
Ethyl 6-Hexadecylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (14)
Colorless oil; Rf 0.46 (hexane : ethyl acetate, 4 : 1); [a]2D0 226.48 (c 0.125,
chloroform); MS (FAB) ¼ m/z 570 (M þ H)þ; IR (Neat) nmax cm21: 3347, 1726;
1H NMR (200 MHz, CDCl3): d 5.55 (d, J ¼ 5.1 Hz, 1H, H-1), 4.58 (dd, J ¼ 8.0 and
2.2 Hz, 1H, H-3), 4.35 (dd, J ¼ 8.0 and 1.4 Hz, 1H, H-4), 4.30 (dd, J ¼ 5.1 and 2.2 Hz, 1H,
H-2), 4.12 (q, J ¼ 7.1 Hz, 2H, –OCH2), 3.85 (dd, J ¼ 7.2 and 1.4 Hz, 1H, H-5), 3.25–3.16
(m, 1H, H-6), 2.71–2.44 (m, 4H, NHCH2 and H-7), 1.72 (bs, 1H, NH), 1.51, 1.44, 1.32
[each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.28–1.21 (m, 31H, 14 ꢀ CH2 and –OCH2CH3), 0.87
(t, J ¼ 6.6 Hz, 3H, –CH2CH3); 13C NMR (CDCl3): d 173.1, 109.3, 108.7, 96.9, 71.3, 69.1,
60.4, 54.5, 47.3, 35.6, 32.3, 30.8, 30.0, 29.9, 29.7, 27.6, 26.4, 25.3, 24.7, 23.0, 20.4,
14.6, 14.4.
Anal. Calcd for C32H59NO7: C, 67.48, H, 10.36, N, 2.46. Found: C, 67.48, H, 10.41,
N, 2.45.
Ethyl 6-Hexadecylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
a-D-glycero-D-galacto-octopyranuronate (14a)
Colorless oil; Rf 0.63 (hexane : ethyl acetate, 4 : 1); [a]2D0 235.98 (c 0.287,
chloroform); MS (FAB) ¼ m/z 570 (M þ H)þ; IR (Neat) nmax cm21: 3350, 1727;
1H NMR (300 MHz, CDCl3): d 5.49 (d, J ¼ 5.1 Hz, 1H, H-1), 4.57 (dd, J ¼ 8.1 and
2.1 Hz, 1H, H-3), 4.43 (dd, J ¼ 8.1 and 1.2 Hz, 1H, H-4), 4.26 (dd, J ¼ 5.1 and 2.1 Hz, 1H,
H-2), 4.12 (q, J ¼ 7.2 Hz, 2H, –OCH2), 3.68 (d, J ¼ 8.4 Hz, 1H, H-5), 3.24–3.18 (m, 1H,
H-6), 2.78 (dd, J ¼ 16.4 and 4.2 Hz, 1H, H-7A), 2.61 (t, J ¼ 6.9 Hz, 2H, NHCH2), 2.45
(dd, J ¼ 16.4 and 7.5 Hz, 1H, H-7B), 1.57 (bs, 1H, NH), 1.49, 1.44, 1.34, 1.30 [each s, each
3H, 2 ꢀ C(CH3)2], 1.27–1.23 (m, 31H, 14 ꢀ CH2 and –OCH2CH3), 0.87 (t, J ¼ 6.9 Hz,
3H, –CH2CH3); 13C NMR (CDCl3): d 172.7, 109.5, 108.9, 97.1, 72.0, 71.4, 71.0,
68.8, 60.6, 56.0, 47.5, 36.0, 32.3, 30.6, 30.0, 29.9, 29.8, 27.7, 27.3, 26.4, 25.4, 24.7, 23.0,
14.6, 14.4.
Anal. Calcd for C32H59NO7: C, 67.48, H, 10.36, N, 2.46. Found: C, 67.47, H, 9.96,
N, 2.65.

ORDER
REPRINTS
62
Katiyar, Mishra, and Tripathi
Ethyl 6-Oleylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (15)
Colorless oil; Rf 0.51 (hexane : ethyl acetate, 3 : 2); [a]2D0 228.58 (c 0.625,
chloroform); MS (FAB) ¼ m/z 596 (M þ H)þ; IR (Neat) nmax cm21: 3367, 1734, 1660;
1H NMR (200 MHz, CDCl3): d 5.55 (d, J ¼ 5.0 Hz, 1H, H-1), 5.36–5.32 (m, 2H,
CH55CH), 4.59 (dd, J ¼ 7.9 and 2.1 Hz, 1H, H-3), 4.35 (d, J ¼ 7.9 Hz, 1H, H-4), 4.30 (dd,
J ¼ 5.0 and 2.1 Hz, 1H, H-2), 4.12 (q, J ¼ 7.2 Hz, 2H, –OCH2), 3.85 (d, J ¼ 7.1 Hz, 1H,
H-5), 3.24–3.20 (m, 1H, H-6), 2.71–2.49 (m, 4H, NHCH2 and H-7), 2.0 (m, 4H,
CH2CH55CHCH2), 1.68 (bs, 1H, NH), 1.51, 1.48, 1.32 [each s, 3H, 3H, 6H,
2 ꢀ C(CH3)2], 1.28–1.21 (m, 27, 12 ꢀ CH2 and –OCH2CH3), 0.88 (t, J ¼ 7.1Hz,
3H,–CH2CH3); 13C NMR (CDCl3): d 172.7, 130.7, 130.3, 109.6, 108.9, 97.1, 72.0, 71.5,
71.2, 68.8, 60.6, 56.1, 47.5, 36.0, 32.9, 32.3, 30.8, 30.6, 30.1, 30.1, 29.9, 29.7, 29.5, 27.7,
27.6, 26.4, 25.4, 24.7, 23.0, 14.6, 14.4.
Anal. Calcd for C34H61NO7: C, 68.57, H, 10.25, N, 2.35. Found: C, 68.57, H, 10.26,
N, 2.36.
Ethyl 6-Benzylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
b-L-glycero-D-galacto-octopyranuronate (16)
Colorless oil; Rf 0.45 (hexane : ethyl acetate, 3 : 2); [a]2D0 245.18 (c 0.375,
chloroform); MS (FAB) ¼ m/z 436 (M þ H)þ; IR (Neat) nmax cm21: 3345, 1726, 1599;
1H NMR (200 MHz, CDCl3): d 7.34–7.20 (m, 5H, ArH), 5.55 (d, J ¼ 5.0 Hz, 1H, H-1),
4.60 (dd, J ¼ 7.8 and 2.2 Hz, 1H, H-3), 4.37 (dd, J ¼ 7.8 and 1.5 Hz, 1H, H-4), 4.21
(dd, J ¼ 5.0 and 2.2 Hz, 1H, H-2), 4.13 (q, J ¼ 7.1 Hz, 2H, –OCH2CH3), 3.95–3.71
(m, 3H, H-5 and CH2C6H5), 3.35–3.25 (m, 1H, H-6), 2.71 and 2.53 (each, dd, J ¼ 15.3
and 5.6 Hz, each 1H, H-7A and H-7B), 1.83 (bs, 1H, NH), 1.51, 1.41, 1.32 [each s, 3H, 3H,
6H, 2 ꢀ C(CH3)2], 1.25 (t, J ¼ 7.1 Hz, 3H, –OCH2CH3); 13C NMR (CDCl3): d 172.5,
141.0, 128.6, 128.5, 127.1, 109.6, 109.0, 97.0, 71.9, 71.5, 71.0, 69.0, 60.7, 55.2, 51.4, 35.9,
26.4, 25.4, 24.7, 14.6.
Anal. Calcd for C23H33NO7: C, 63.44, H, 7.58, N, 3.21. Found: C, 63.41, H, 7.60,
N, 3.22.
Ethyl 6-Benzylamino-6,7-dideoxy-1,2 : 3,4-di-O-isopropylidene-
a-D-glycero-D-galacto-octopyranuronate (16a)
Colorless oil; Rf 0.65 (hexane : ethyl acetate, 3 : 2); [a]2D0 278.28 (c 0.225,
chloroform); MS (FAB) ¼ m/z 436 (M þ H)þ; IR (Neat) nmax cm21: 3350, 1728, 1600;
1H NMR (300 MHz, CDCl3): d 7.34–7.21 (m, 5H, ArH), 5.50 (d, J ¼ 5.0 Hz, 1H, H-1),
4.59 (dd, J ¼ 8.0 and 2.0 Hz, 1H, H-3), 4.53 (dd, J ¼ 8.0 and 1.2 Hz, 1H, H-4), 4.26 (dd,
J ¼ 5.0 and 2.0 Hz, 1H, H-2), 4.11 (q, J ¼ 7.2 Hz, 2H, –OCH2CH3), 3.85 (s, 2H,
CH2C6H5), 3.75 (d, J ¼ 8.4 Hz, 1H, H-5), 3.32–3.28 (m, 1H, H-6), 2.81 (dd, J ¼ 15.9 and
3.9 Hz, 1H, H-7A), 2.49 (dd, J ¼ 15.9 and 7.2 Hz, 1H, H-7B), 1.65 (bs, 1H, NH), 1.50, 1.43,
1.35, 1.31 [each s, each 3H, 2 ꢀ C(CH3)2], 1.25 (t, J ¼ 7.2 Hz, 3H, –OCH2CH3);

ORDER
REPRINTS
Galactopyranosyl Amino Esters
63
13C NMR (CDCl3): d 173.0, 141.2, 128.6, 127.2, 109.3, 108.7, 96.9, 71.4, 69.2, 60.5, 54.3,
51.8, 35.6, 26.4, 25.4, 24.7, 14.6.
Anal. Calcd for C23H33NO7: C, 63.44, H, 7.58, N, 3.21. Found: C, 63.55, H, 7.68,
N, 3.30.
Ethyl 6-(3,4-Dimethoxyphenylmethyl)amino-6,7-Dideoxy-1,2 : 3,4-di-
O-isopropylidene-b-L-glycero-D-galacto-octopyranuronate (17)
General Method
Ethyl-6,7-dideoxy-6-amino-b-L-glycero-1,2 : 3,4-di-O-isopropylidene-a-D-galacto-oct-
opyranuronate 5 (1.5 g, 4.34mmol) was dissolved in a mixture of trimethyl orthoformate and
dichloromethane (2: 5) and stirred magnetically at 08C. 3,4 dimethoxybenzaldehyde
(0.5mL, 4.5 mmol) was added and stirring continued for another 4 hr at the same
temperature. NaCNBH3 (0.26g, 4.34mmol) was added to the stirring reaction mixture and
stirring continued for 12hr at 308C. Solvent evaporated under reduced pressure and the
residue was dissolved in ethyl acetate and washed with aqueous NH4Cl (2 ꢀ 25mL)
followed by water (2 ꢀ 20mL). It was dried (Na2SO4) and evaporated under reduced
pressure to give the crude mass, which was chromatographed over SiO2 column using
hexane : ethyl acetate (4 : 1) as eluent to give title compound. Yield: (80%); Colorless oil; Rf
0.35 (hexane : ethyl acetate, 4 : 1); [a]2D0 248.38 (c 0.087, chloroform); MS (FAB) ¼ m/z 496
(M þ H)þ; IR (Neat) nmax cm21: 1726; 1H NMR (200MHz, CDCl3): d 6.93–6.80 (m, 3H,
ArH), 5.56 (d, J ¼ 5.0 Hz, 1H, H-1), 4.59 (dd, J ¼ 8.0 and 2.0 Hz, 1H, H-3), 4.37
(d, J ¼ 8.0 Hz, 1H, H-4), 4.31 (dd, J ¼ 5.0 and 2.0 Hz, 1H, H-2), 4.13 (q, J ¼ 7.1 Hz, 2H, –
OCH2), 3.96–3.68 (m, 9H, NCH2, 2 ꢀ Ar-OCH3 and H-5), 3.32–3.29 (m, 1H, H-6), 2.70
and 2.52 (each dd, J ¼ 16.8 and 5.5 Hz, each 1H, H-7A and H-7B), 1.87 (bs, 1H, NH), 1.52,
1.41, 1.32 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.25 (t, J ¼ 7.2 Hz, 3H, –OCH2CH3); 13C
NMR (CDCl3): d 172.5, 149.3, 148.3, 133.6, 120.7, 112.0, 111.4, 109.6, 109.0, 97.0, 71.9,
71.5, 71.0, 69.0, 60.7, 56.3, 56.1, 55.0, 51.0, 35.8, 26.3, 25.3, 24.8, 14.6.
Anal. Calcd for C25H37NO9: C, 60.60, H, 7.47, N, 2.82. Found: C, 60.58, H, 7.47,
N, 2.81.
Ethyl 6-(2-Hydroxyphenylmethyl)amino-6,7-Dideoxy-1,2 : 3,4-di-
O-isopropylidene-b-L-glycero-D-galacto-octopyranuronate (18)
Yield: (70%); Colorless oil; Rf 0.40 (hexane : ethyl acetate, 4 : 1); [a]2D0 224.98
(c 0.125, chloroform); MS (FAB) m/z ¼ 436 (M þ H)þ; IR (Neat) nmax cm21: 1726;
1H NMR (200 MHz, CDCl3): d 8.41 (bs, 1H, Ar-OH), 7.31–7.24 and 6.94–6.81 (each m,
each 2H, ArH), 5.47 (d, J ¼ 4.9 Hz, 1H, H-1), 4.63 (dd, J ¼ 7.9 and 2.3 Hz, 1H, H-3), 4.39
(d, J ¼ 7.9 Hz, 1H, H-4), 4.29 (dd, J ¼ 4.9 and 2.3 Hz, 1H, H-2), 4.16–3.81
(m, 6H, –OCH2, –NCH2,, H-5, H-6), 2.92–2.70 (m, 2H, H-7), 1.55 (bs, 1H, NH), 1.50,
1.47, 1.35 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.19 (t, J ¼ 7.2 Hz, 3H, –OCH2CH3); 13
C
NMR (CDCl3): d 171.9, 168.8, 161.5, 132.9, 132.3 119.1, 117.3, 109.6, 109.1, 97.0, 71.2,
71.1, 70.7, 69.3, 65.3, 60.7, 38.2, 26.5, 26.4, 25.3, 24.8, 14.6.
Anal. Calcd for C23H33NO8: C, 61.19, H, 7.31, N, 3.10. Found: C, 61.20, H, 7.31, N, 3.08.

ORDER
REPRINTS
64
Katiyar, Mishra, and Tripathi
(1R, 2R, 3S, 4S, 5R, 6S) Ethyl [6,7-Dideoxy-6-fN3-(4-Chlorophenyl)-
(1-Ureidyl)g-1,2 : 3,4-di-O-Isopropylidene-tetrahydro-
1,5-octopyranos-5-yl]-uronate (19)
The amino ester 5 (0.50 g, 1.44mmol) and p-chlorophenyl isocyanate (0.23 g, 1.5 mmol)
in anhydrous dichloromethane (15.0 mL) was magnetically stirred at 258C for 7 hr. Solvent
was evaporated and the reaction mixture was chromatographed over SiO2 column using a
gradient of hexane : ethyl acetate (4: 1) as eluent to give title compound. yield: 0.50g (69%);
colorless oil; Rf 0.40 (hexane : ethyl acetate, 7 : 3); [a]2D0 220.68 (c 0.087, chloroform); MS
1
(FAB) ¼ m/z 500, (M þ H)þ; IR (Neat) nmax cm21: 3341, 1726, 1657, 1545; H NMR
(200MHz, CDCl3): d 7.30–7.18 (m, 4H, ArH), 6.74 (s, 1H, –NHAr), 5.56 (d, J ¼ 4.9 Hz,
1H, H-1), 5.44 (d, J ¼ 7.7 Hz, 1H, –NHCO), 4.60 (dd, J ¼ 7.8 and 2.3 Hz, 1H, H-3), 4.32
(dd, J ¼ 4.9 and 2.3 Hz, 1H, H-2), 4.25 (dd, J ¼ 7.8 and 1.6 Hz, 1H, H-4), 4.17–4.02
(m, 4H, –OCH2,, H-5 and H-6), 2.85 and 2.75 (each dd, J ¼ 17.0 and 5.2 Hz, each 1H, H-7A
and H-7B), 1.52, 1.41, 1.32 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.20 (t, J ¼ 7.2 Hz, 3H, –
OCH2CH3); 13C NMR (CDCl3): d 173.0, 155.8, 138.3, 129.3, 128.3, 121.8, 109.8, 109.2,
96.8, 71.8, 71.2, 71.1, 68.1, 61.0, 48.4, 35.9, 26.3, 25.3, 24.8, 14.5.
Anal. Calcd for C23H31N2O8Cl: C, 55.31, H, 6.21, N, 5.61. Found: C, 55.44, H, 6.21,
N, 5.59.
(1R, 2R, 3S, 4S, 5R, 6S) Ethyl [6,7-Dideoxy-6-fN3-Benzyl-N1-cyclopropyl-
(1-Ureidyl)g-1,2 : 3,4-di-O-Isopropylidene-tetrahydro-1,5-octopyranos-
5-yl]-uronate (20)
It was obtained by the reaction of 6 (250 mg, 0.65 mmol) with benzyl isocyanate
(86.4 mg, 0.65 mmol) as described above. Yield: 0.33 g (95%); Colorless solid, mp 108–
1108C; Rf 0.51 (hexane : ethyl acetate, 7 : 3); [a]2D0 2498 (c 0.20, chloroform); MS
1
(FAB) ¼ m/z 519 (M þ H)þ; IR (Neat) nmax cm21: 3452, 1731, 1656, 1515; H NMR
(200 MHz, CDCl3): d 7.31–7.22 (m, 5H, ArH), 5.48 (d, J ¼ 5.0 Hz, 1H, H-1), 4.60 (dd,
J ¼ 8.0 and 2.5 Hz, 1H, H-3), 4.45 and 4.39 (each d, J ¼ 6.0 Hz, each 1H, NCHA and
NCHB), 4.28 (dd, J ¼ 5.0 and 2.5 Hz, 1H, H-2), 4.20–4.08 (m, 4H, H-4, –OCH2 and H-5),
3.77–3.74 (m, 1H, H-6), 3.44–3.37 (m, 1H, NCH), 2.74–2.58 (m, 2H, H-7), 1.60 (s, 1H,
NH), 1.46, 1.32, 1.29 [each s, 6H, 3H, 3H, 2 ꢀ C(CH3)2], 1.22 (t, J ¼ 7.1 Hz, OCH2CH3),
0.78–0.48 (m, 4H, cyclopropyl ring protons); 13C NMR (CDCl3): d 172.5, 159.0, 140.6,
129.0, 127.6, 127.2, 110.0, 109.7, 97.0, 71.6, 71.5, 70.9, 68.0, 60.6, 44.4, 35.4, 26.4, 25.6,
25.0, 14.6, 9.9, 8.8.
Anal. Calcd for C27H38N2O8: C, 62.54; H, 7.33; N, 5.40. Found: C, 62.52; H, 7.23;
N, 5.40.
(1R, 2R, 3S, 4S, 5R, 6S) Ethyl [6,7-Dideoxy-6-fN3-Benzyl-N1-dodecyl-
(1-Ureidyl)g-1,2 : 3,4-di-O-Isopropylidene-tetrahydro-1,5-octopyranos-
5-yl]-uronate (21)
It was obtained by the reaction of 13 (0.70 g, 1.36 mmol) with benzyl isocyanate
(0.19 g, 1.45 mmol) as described above. Yield: 0.84 g (95%); colorless foam; Rf 0.65

ORDER
REPRINTS
Galactopyranosyl Amino Esters
65
(hexane : ethyl acetate, 3 : 2); [a]2D0 229.78 (c 0.0875, chloroform); MS (FAB) ¼ m/z 647
1
(M þ H)þ; IR (Neat) nmax cm21: 2927, 1727, 1645, 1536, 1460; H NMR (200 MHz,
CDCl3): d 7.31–7.26 (m, 5H, ArH), 5.48 (d, J ¼ 5.0 Hz, 1H, H-1), 4.59 (dd, J ¼ 7.7 and
2.0 Hz, 1H, H-3), 4.45 and 4.35 (each d, J ¼ 5.7 Hz, each 1H, NCHA and NCHB), 4.28 (dd,
J ¼ 5.0 and 2.0 Hz, 1H, H-2), 4.19–4.06 (m, 5H, H-4, –OCH2, H-5 and H-6), 3.21–3.13
(m, 3H, NCH2 and H-7A), 2.71 (dd, J ¼ 15 and 4.0 Hz, 1H, H-7B), 1.62 (s, 1H, NH),
1.47, 1.39, 1.30 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.28–1.20 (m, 23H, CH2s
and –OCH2CH3), 0.88 [t, J ¼ 6.7 Hz, 3H, –(CH2)11CH3].
Anal. Calcd for C36H58N2O8: C, 66.87, H, 8.98, N, 4.33. Found: C, 67.12, H, 9.0,
N, 4.25.
(1R, 2R, 3S, 4S, 5R, 6S) Ethyl [6,7-Dideoxy-6-fN3-(4-Chlorophenyl),
N1-Oleyl-(1-Ureidyl)g-1,2 : 3,4-di-O-Isopropylidene-tetrahydro-
1,5-octopyranos-5-yl]-uronate (22)
It was obtained by the reaction of 15 (0.60 g, 1.00 mmol) with 4-Cl-phenyl isocyanate
(0.16 g, 1.1 mmol) as described above. Yield: 0.72 g (95%), colorless foam; Rf 0.55
(hexane : ethyl acetate, 7 : 3); [a]2D0 2308 (c 0.15, chloroform); MS (FAB) ¼ m/z 750
1
(M þ H)þ; IR (Neat) nmax cm21: 3019, 2928, 1724, 1663, 1520; H NMR (200 MHz,
CDCl3): d 7.30–7.17 (m, 4H, ArH), 5.53 (d, J ¼ 5.0 Hz, 1H, H-1), 5.36–5.34 (m, 2H,
CH55CH), 4.62 (dd, J ¼ 7.7 and 2.3 Hz, 1H, H-3), 4.34–4.31 (m, 2H, H-2 and H-4),
4.22–4.11 (m, 4H, –OCH2, H-5 and H-6), 2.76–2.71 (m, 2H, H-7), 1.90–2.10 (m, 4H,
CH2CH55CHCH2), 1.50, 1.42, 1.32 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.26–1.21
(m, 26H, CH2s and –OCH2CH3), 0.87 [t, J ¼ 6.7 Hz, 3H, (CH2)7CH3].
Anal. Calcd for C41H65N2O8Cl: C, 65.68, H, 8.68, N, 3.74. Found: C, 66.65, H, 8.66,
N, 3.72.
(1R, 2R, 3S, 4S, 5R, 6S) Ethyl [6,7-Dideoxy-6-fN3-(4-Chlorophenyl)-
N1-Benzyl-(1-Ureidyl)g-1,2 : 3,4-di-O-Isopropylidene-tetrahydro-
1,5-octopyranos-5-yl]-uronate (23)
It was obtained by the reaction of 16 (0.70 g, 1.61 mmol) with 4-Cl-phenyl isocyanate
(0.25 g, 1.64 mmol) as described above. Yield: 0.93 g (98%); colorless foam; Rf 0.40
(hexane : ethyl acetate, 4 : 1); [a]2D0 242.28 (c 0.175, chloroform); MS (FAB) ¼ m/z 590
1
(M þ H)þ; IR (Neat) nmax cm21: 2990, 2931, 1725, 1598, 1527; H NMR (200 MHz,
CDCl3): d 7.33–7.16 (m, 9H, ArH), 5.58 (d, J ¼ 5.0 Hz, 1H, H-1), 4.80 (bs, 1H, Ar-NH),
4.63 (dd, J ¼ 7.8 and 2.3 Hz, 1H, H-3), 4.34 (dd, J ¼ 5.0 and 2.3 Hz, 1H, H-2), 4.22
(d, J ¼ 7.8 Hz, 1H, H-4), 4.03–4.13 (m, 6H, –OCH2, –NCH2, H-5 and H-6), 2.89–2.51
(m, 2H, H-7), 1.53, 1.42, 1.33 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 1.18 (t, J ¼ 7.1 Hz,
3H, –OCH2CH3); 13C NMR (50 MHz, CDCl3): d 172.0, 157.7, 139.1, 138.7, 129.1, 128.9,
127.5, 120.9, 110.1, 109.2, 96.9, 71.69, 71.63, 70.92, 67.8, 61.3, 53.8, 49.2, 35.3, 26.4,
26.3, 25.3, 14.4.
Anal. Calcd for C30H37N2O8Cl: C, 61.17, H, 6.28, N, 4.75. Found: C, 61.20, H, 6.31,
N, 4.72.

ORDER
REPRINTS
66
Katiyar, Mishra, and Tripathi
(1R, 2R, 3S, 4S, 5R, 6S) Ethyl [6,7-Dideoxy-6-fN3-Benzyl-N1-(3,4-
Dimethoxyphenyl methyl)-(1-Ureidyl)g-1,2 : 3,4-di-O-Isopropylidene-
tetrahydro-1,5-octopyranos-5-yl]-uronate (24)
It was obtained by the reaction of 17 (0.50 g, 1.01 mmol) with benzyl isocyanate
(0.16 g, 1.1 mmol) as described above. Yield: 0.62 g (98%); colorless foam; Rf 0.40
(hexane : ethyl acetate 4 : 1); [a]2D0 240.78 (c 0.15, chloroform); MS (FAB) ¼ m/z 629
(M þ H)þ; IR (Neat) nmax cm21: 3422, 1728, 1644, 1518, 1459, 1254; 1H NMR
(200 MHz, CDCl3): d 7.35–7.19 (m, 5H, ArH), 6.79–6.76 (m, 2H, ArH), 5.54
(d, J ¼ 5.0 Hz, 1H, H-1), 4.61 (dd, J ¼ 7.9 and 2.3 Hz, 1H, H-3), 4.53–4.40 (m, 4H,
N1CH2 and NHCH2), 4.34 (d, J ¼ 7.9 Hz, 1H, H-4), 4.30 (dd, J ¼ 5.0 and 2.3 Hz, 1H,
H-2), 4.23 (d, J ¼ 7.9 Hz, 1H, H-5), 4.06 (q, J ¼ 7.2 Hz, 2H, –OCH2), 3.88–3.78 (m, 9H,
2 ꢀ ArOCH3, N3CH2 and H-6), 3.0 and 2.7 (each d, J ¼ 16.5 Hz, each 1H, H-7A and
H-7B), 1.47, 1.41, 1.31 [each s, 3H, 3H, and 6H, 2 ꢀ (CH3)2], 1.18 (t, J ¼ 7.4 Hz, 3H,
OCH2CH3).
Anal. Calcd for C33H44N2O10: C, 63.06, H, 7.06, N, 4.46. Found: C, 63.12, H, 7.10,
N, 4.48.
(10R, 20R, 30S, 40S, 50R, 6S) N3-(4-Chlorophenyl)-5,6-Dihydro-6-
(10,20 : 30,40-di-O-Isopropylidene-10,20,30,40-tetrahydro-10,50-Pyranos-50-yl)-
pyrimidin-2,4-dione (25)
˚
A mixture of compound 19 (0.30 g, 0.60 mmol), 4 A MS (0.03 g), TBAB (0.03 g,
0.093 mmol) and DBU (0.086 mL, 0.564 mmol) in anhydrous toluene (15 mL) was
refluxed for 2 hr. Solvent was evaporated and the residue was chromatographed over a
SiO2 column using a gradient of hexane : ethyl acetate (3 : 1) as eluent to give title
compound. Yield: 0.19 g (70%); colorless foam; Rf 0.30 (hexane : ethyl acetate, 3 : 2);
[a]2D5 251.88 (c 0.3125, chloroform); MS (FAB) m/z ¼ 454 (M þ H)þ; IR (Neat) nmax
1
cm21: 3393, 1661, 1598, 1554, 1495, 1384; H NMR (200 MHz, CDCl3): d 7.26–7.11
(m, 4H, ArH), 5.54 (d, J ¼ 4.4 Hz, 1H, H-10), 4.57 (d, J ¼ 7.1 Hz, 1H, H-30), 4.28–4.06
(m, 4H, H-20, H-40, H-50, H-6), 2.71–2.76 (m, 2H, H-5), 1.47, 1.38, 1.29 [each s, 3H, 3H,
and 6H, 2 ꢀ (CH3)2]; 13C NMR (50 MHz, CDCl3): d 172, 168, 137.9, 121.6, 120.7, 109.9,
109.4, 96.8, 71.6, 71.3, 71.0, 53.7, 34.1, 26.3, 25.3, 24.6.
Anal. Calcd for C21H25N2O7Cl: C, 55.62, H, 5.52, N, 6.18. Found: C, 55.70, H, 5.72,
N, 6.14.
(10R, 20R, 30S, 40S, 50R, 6S) N3-Benzyl-N1-cyclopropyl-5,6-dihydro-
6-(10,20 : 30,40-di-O-Isopropylidene-10,20,30,40-tetrahydro-
10,50-pyranos-50-yl)-Pyrimidin-2,4-dione (26)
It was obtained from 20 (0.20 g, 0.39 mmol) as described in general procedure. Yield:
0.14 g (75%); colorless solid, mp 123–1258C; Rf 0.54 (hexane : ethyl acetate 3 : 2); [a]D25
þ3.28 (c 0.125, chloroform); MS (FAB) ¼ m/z 473 (M þ H)þ; IR (Neat) nmax cm21
:
1713, 1671, 1436; 1H NMR (200 MHz, CDCl3): d 7.26–7.19 (m, 5H, ArH), 5.47
(d, J ¼ 5.0 Hz, 1H, H-1), 4.89 (s, 2H, NCH2Ar), 4.56 (dd, J ¼ 7.8 and 2.4 Hz, 1H, H-3),

ORDER
REPRINTS
Galactopyranosyl Amino Esters
67
4.25 (dd, J ¼ 5.0 and 2.4 Hz, 1H, H-2), 4.18 (d, J ¼ 7.8 Hz, 1H, H-4), 3.85–3.73 (m, 2H,
H-5 and H-6), 3.01–2.82 (m, 2H, H-5A and NCH), 2.71 (dd, J ¼ 17.0 and 5.8 Hz, 1H,
H-5B), 1.57, 1.44, 1.29 [each s, 3H, 3H, 6H, 2 ꢀ C(CH3)2], 0.97–0.52 (m, 4H, cyclopropyl
ring protons); 13C NMR (CDCl3): d 168.9, 154.2, 138.0, 129.7, 128.7, 127.6, 110.2, 109.2,
96.7, 71.2, 71.0, 70.6, 68.8, 54.0, 44.4, 34.3, 32.2, 26.2, 25.2, 24.7, 10.3, 6.6.
Anal. Calcd for C25H32N2O7: C, 63.56; H, 6.78; N, 5.93. Found: C, 63.52; H, 6.78;
N, 5.90.
(10R, 20R, 30S, 40S, 50R, 6S)-N3-Benzyl-N1-dodecyl-5,6-dihydro-6-
(10,20 : 30,40-di-O-Isopropylidene-10,20,30,40-tetrahydro-10,50-pyranos-50-yl)-
Pyrimidin-2,4-dione (27)
It was obtained from 21 (0.40 g, 0.62 mmol) as described in general procedure. Yield:
0.33 g (89%); colorless foam; Rf 0.55 (hexane : ethyl acetate 3 : 2); [a]2D5 220.58 (c 0.4,
chloroform); MS (FAB) ¼ m/z 601 (M þ H)þ; IR (Neat) nmax cm21: 1727, 1648, 1518,
1461, 1379; 1H NMR (200 MHz, CDCl3): d 7.45–7.42 (m, 2H, ArH), 7.26–7.22 (m, 3H,
ArH), 5.43 (d, J ¼ 5.0 Hz, 1H, H-10), 4.90 (s, 2H, NCH2Ar), 4.61 (dd, J ¼ 7.6 and 2.3 Hz,
1H, H-30), 4.33 (dd, J ¼ 5.0 and 2.3 Hz, 1H, H-20), 3.95 (d, J ¼ 7.6 Hz, 1H, H-40), 3.81
(m, 1H, NCHA), 3.69–4.10 (m, 2H, H-50 and H-6), 3.30–2.90 (m, 1H, NCHB), 2.89–2.70
(m, 2H, H-5), 1.50 (m, 2H, –NCH2 CH2), 1.44, 1.29 [each s, each 3H, C(CH3)2], 1.25
(m, 18H, 9 ꢀ CH2), 1.09 [s, 6H, C(CH3)2], 0.87 (t, J ¼ 7.6 Hz, 3H, CH2CH3); 13C NMR
(50 MHz, CDCl3): d 169.1, 152.9, 138.1, 129.5, 128.7, 127.6, 110.1, 109.2, 96.5, 71.1,
70.9, 70.5, 69.4, 52.5, 50.0, 44.4, 34.2, 32.1, 30.0, 29.9, 29.7, 29.7, 28.6, 27.3, 26.3, 26.1,
25.2, 24.7, 14.5.
Anal. Calcd for C34H52N2O7: C, 68.0, H, 8.67, N, 4.67. Found: C, 68.23, H, 8.91,
N, 4.68.
(10R, 20R, 30S, 40S, 50R, 6S)-N3-(4-Chlorophenyl)-N1-Oleyl-5,6-dihydro-
6-(10,20 : 30,40-di-O-Isopropylidene-10,20,30,40-tetrahydro-
10,50-pyranos-50-yl)-Pyrimidin-2,4-dione (28)
It was obtained from 22 (0.50 g, 0.67 mmol) as described in general procedure. Yield:
0.42 g (90%); colorless foam; Rf 0.40 (hexane : ethyl acetate 3 : 2); [a]2D5–10.98 (c 0.2375,
chloroform); MS (FAB) ¼ m/z 704 (M þ H)þ; IR (Neat) nmax cm21: 1710, 1593, 1473,
1351; 1H NMR (200 MHz, CDCl3): d 7.37 (d, J ¼ 8.4 Hz, 2H, ArH), 7.10 (d, J ¼ 8.4 Hz,
2H, ArH), 5.55 (d, J ¼ 5.0 Hz, 1H, H-10), 5.37–5.34 (m, 2H, CH55CH), 4.61 (dd, J ¼ 8.0
and 2.2 Hz, 1H, H-30), 4.33 (dd, J ¼ 5.0 and 2.2 Hz, 1H, H-20), 4.25(d, J ¼ 8.0 Hz, 1H,
H-40), 4.02–3.81 (m, 3H, H-50, NCHA and H-6), 3.24–2.96 (m, 2H, H-5B and NCHB),
2.02–1.99 (m, 4H, CH2CH55CHCH2), 1.63–1.61 (m, 2H, NCH2), 1.46 and 1.34 (each s,
each 6H, 2 ꢀ (CH3)2), 1.33–1.16 (m, 13 ꢀ CH2), 0.88 (t, J ¼ 7.2 Hz, 3H, CH2CH3);
13C NMR (50 MHz, CDCl3): d 168.8, 152.6, 134.4, 130.4, 129.4, 110.2, 109.2, 96.8, 71.2,
70.9, 70.5, 68.0, 52.4, 50.1, 34.5, 32.3, 30.1, 29.7, 28.4, 27.7, 26.7, 26.3, 25.1, 14.5.
Anal. Calcd for C39H59N2O7Cl: C, 66.57, H, 8.4, N, 3.98. Found: C, 66.95, H, 8.44,
N, 3.92.

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Katiyar, Mishra, and Tripathi
(10R, 20R, 30S, 40S, 50R, 6S)-N1-Benzyl-N3-(4-Chlorophenyl)-5,6-Dihydro-
6-(10,20 : 30,40-di-O-Isopropylidene-10,20,30,40-tetrahydro-10,50-pyranos-
50-yl)-Pyrimidin-2,4-dione (29)
It was obtained from 23 (0.40 g, 0.68 mmol) as described above. Yield: 0.34 g
(92%); Colorless foam; Rf 0.55 (hexane : ethyl acetate, 3 : 2); [a]2D5 þ48 (c 0.075,
chloroform); MS (FAB) ¼ m/z 544 (M þ H)þ; IR (Neat) nmax cm21: 1685, 1593,
1
1373; H NMR (200 MHz, CDCl3): d 7.39 (dd, J ¼ 11.3 and 2.6 Hz, 2H, ArH), 7.41–
7.33 (m, 5H, ArH), 7.18–7.12 (m, 3H, ArH), 7.15 (dd, J ¼ 11.3 and 2.6 Hz, 2H, ArH),
5.62 (d, J ¼ 5.1 Hz, 1H, H-10), 5.42 and 4.24 (two d, J ¼ 14.9 Hz, each 1H, NCHA and
NCHB), 4.62 (dd, J ¼ 7.8 and 2.4 Hz, 1H, H-30), 4.36 (dd, J ¼ 5.1 and 2.4 Hz, 1H,
H-20), 4.20 (dd, J ¼ 7.8 and 1.8 Hz, 1H, H-40), 4.05 (dd, J ¼ 9.0 and 1.8 Hz, 1H, H-50),
3.89–3.84 (m, 1H, H-6), 2.90–2.82 (m, 2H, H-5), 1.48, 1.44, 1.34, 1.31 [each s, each
3H, 2 ꢀ (CH3)2]; 13C NMR (50 MHz, CDCl3): d 168.7, 153.2, 137.6, 134.5, 134.4,
130.4, 129.5, 129.2, 128.9, 128.2, 110.2, 109.3, 96.8, 71.2, 70.9, 70.5, 69.2, 52.4, 50.5,
34.6, 26.7, 26.3, 25.1, 24.9.
Anal. Calcd for C28H31N2O7Cl: C, 61.87, H, 5.71, N, 5.16. Found: C, 62.26, H, 5.91,
N, 5.03.
(10R, 20R, 30S, 40S, 50R, 6S)-N3-Benzyl-N1-(3,4-Dimethoxy phenylmethyl)-
5,6-Dihydro-6-(10,20 : 30,40-di-O-Isopropylidene-10,20,30,40-tetrahydro-
10,50-pyranos-50-yl)-Pyrimidin-2,4-dione (30)
It was obtained from 24 (0.50 g, 0.80 mmol) as described in general procedure. Yield:
0.44 g (95%); colorless foam; Rf 0.35 (hexane : ethyl acetate, 3 : 2); MS (FAB) ¼ m/z 583
(M þ H)þ; [a]D25 28.348 (c 0.285, chloroform); IR (Neat) nmax cm21: 1710, 1596, 1461,
1355; 1H NMR (200 MHz, CDCl3): d 7.47 (dd, J ¼ 8.4 and 1.2 Hz, 2H, ArH), 7.30–7.24
(m, 3H, ArH), 6.84–6.81 (m, 3H, ArH), 5.52 (d, J ¼ 5.0 Hz, 1H, H-10), 5.30 and 4.96 (two
d, J ¼ 14.8 Hz, each 1H, NCH2Ar), 4.60 (dd, J ¼ 7.8 and 1.6 Hz, 1H, H-30), 4.36 (dd,
J ¼ 5.0 and 1.6 Hz, 1H, H-20), 4.12 (dd, J ¼ 7.8 and 1.8 Hz, 1H, H-40), 3.83 and 3.86 (each
s, each 3H, Ar-OCH3), 3.75–3.62 (m, 1H, H-6), 2.80 (dd, J ¼ 16.8 and 5.6 Hz, 1H, H-5A),
2.70 (dd, J ¼ 16.8 and 5.6 Hz, 1H, H-5B), 1.46, 1.26, 1.12 [each s, 3H, 3H, 6H,
2 ꢀ (CH3)2]; 13C NMR (50 MHz, CDCl3): d 169.0, 153.2, 130.4, 138.1, 149.1, 149.7,
129.5, 128.8, 127.7, 121.3, 112.1, 111.6, 109.3, 110.1, 96.6, 71.1, 70.5, 69.7, 56.3, 52.0,
50.3, 44.6, 34.2, 26.3, 26.1, 25.2, 24.8.
Anal. Calcd for C31H38N2O9: C, 63.91, H, 6.53, N, 4.81. Found: C, 64.05, H, 6.52,
N, 4.73.
ACKNOWLEDGMENTS
Authors thank Director CDRI for his keen interest in the program and to ICMR, New
Delhi, India and Department of Ocean Development, New Delhi, India for financial
support. We thank RSIC staff for giving spectral data and analysis.

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Received July 2, 2003
Revised September 27, 2003
Accepted September 27, 2003

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