Gold catalyzed glycosidations for the synthesis of sugar acrylate/acrylamide hybrids and their utility

Article abstract of DOI:10.1016/j.carres.2011.04.018

Propargyl glyco 1,2-orthoesters were exploited for the efficient synthesis of interesting glycomonomers such as glyco-acrylates and acrylamides using gold catalysts. It was observed that propargyl glyco 1,2-orthoesters with hydroxyethyl acrylates gives very good yield of the corresponding glyco-acrylates in a single step in the presence of catalytic amount of gold(III) catalyst; whereas, gold catalyzed glycosidation reaction on hydroxyethyl acrylamides was found to yield the corresponding acrylamidoyl 1,2-orthoester which was then converted to the corresponding glycol-acrylamide in the presence of catalytic amount of TMSOTf. Synthesized glyco-acrylate/ acrylamide monomers are shown to undergo thiolate addition as well as free radical polymerization.

Full text of DOI:10.1016/j.carres.2011.04.018

Carbohydrate Research 346 (2011) 1511–1518
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Gold catalyzed glycosidations for the synthesis of sugar
acrylate/acrylamide hybrids and their utility
Shivaji A. Thadke a, Mritunjoy Kar b, Sayam Sen Gupta b, Srinivas Hotha c,
⇑
a Division of Organic Chemistry, Combi Chem-Bio Resource Center, National Chemical Laboratory, Pune 411 008, India
b Division of Chemical Engineering & Process Development, National Chemical Laboratory, Pune 411 008, India
c Department of Chemistry, Indian Institute of Science Education & Research, Pune 411 021, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Available online 23 April 2011
Propargyl glyco 1,2-orthoesters were exploited for the efficient synthesis of interesting glycomonomers
such as glyco-acrylates and acrylamides using gold catalysts. It was observed that propargyl glyco 1,2-
orthoesters with hydroxyethyl acrylates gives very good yield of the corresponding glyco-acrylates in a
single step in the presence of catalytic amount of gold(III) catalyst; whereas, gold catalyzed glycosidation
reaction on hydroxyethyl acrylamides was found to yield the corresponding acrylamidoyl 1,2-orthoester
which was then converted to the corresponding glycol-acrylamide in the presence of catalytic amount of
TMSOTf. Synthesized glyco-acrylate/acrylamide monomers are shown to undergo thiolate addition as
well as free radical polymerization.
Dedicated to Professor Andras Liptak on
occasion of his 75th birthday
Keywords:
Glycopolymers
Carbohydrates
Glycosylation
Glycoacrylates
Glycoacrylamides
Gold
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
To investigate basic roles of carbohydrate moieties of glycocon-
jugates in these interactions, simple model polymers with excel-
Synthetic macromolecules with pendant saccharide residues
are known as glycopolymers which are studied immensely for a
variety of applications such as drug delivery agents, hydrogels,
extracellular matrices for controlled cell culture, supports for chro-
matography, and sometimes as multivalent biological probes.1 In
addition, the multivalent display of pendant glycans is understood
to be beneficial in mimicking natural cell surface oligosaccharides.2
Nature uses glycolipids and glycoproteins effectively in cell signal-
ing, cell–cell differentiation, and communication.3 This happens as
a result of very specific interactions that takes place between the
glycans of the glycoproteins and their corresponding receptors at
the cell surface.4 Multivalent glycolipids and glycoproteins can,
respectively, be defined as glycosides of long chain hydrocarbons
and proteins. Isolation of naturally occurring glycopolymers from
the nature is rather tedious as they exist in the microheterogenous
forms and thus chemical synthesis of their mimics is the most con-
venient and effective route.5 Synthesis of polymers with carbohy-
drate epitopes as pendants is an easy way to mimic glycolipids
and glycoproteins. They also allow us to study the role of polyva-
lency that is known to be responsible for the high specificity of
these glycan–receptor interactions.6
lent solubility in aqueous medium needs to be synthesized from
polymerizable glycomonomers. However, for any useful glycopoly-
mer, the simplicity in backbone structure is essential as it facili-
tates easy understanding of carbohydrate protein interactions.
Further, general synthetic strategies should be designed in such a
way that glycopolymers of various size, shapes, and grafting den-
sity can be synthesized easily.7
Existing methods for the synthesis of glycopolymers can be clas-
sified into two major classes. At the first instance, glycopolymers
are advantageously synthesized by subjecting a sugar residue with
a pendant polymerizable functional group to suitable polymeriza-
tion conditions to obtain good glycosylation density (Fig. 1).8 For
example, glycopolymers can be synthesized by free radical poly-
merization of glycomonomers. The most commonly used glycomo-
nomer for such polymerization reactions are acryloyl and
acrylamido glycosides bearing
x-linker of various lengths. The
resulting glycopolymers formed, such as polyacrylamide glycoside,
is non-toxic and water soluble.8b Further the degree of incorpora-
tion of the oligosaccharide can be varied by copolymerization with
another acrylamide monomer. Similarly, neoglycoproteins can be
synthesized from glyco N-carboxyanhydrides which in turn can
be obtained from amino acid glycoconjugates.8c However, multi-
step synthesis of the monomer, laborious work-up, and purification
are the major limitations.
⇑
Corresponding author.
E-mail address: s.hotha@iiserpune.ac.in (S. Hotha).
0008-6215/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2011.04.018

1512
Method 1:
S. A. Thadke et al. / Carbohydrate Research 346 (2011) 1511–1518
the acrylate mannopyranoside (3a) in 78% yield.12 A similar
= Sugar
= Linker
= Polymerizable Group
= Polymer Backbone
reaction between orthoester 1 and hydroxyethyl methacrylate 2b
enabled the synthesis of corresponding methyl acrylate mannopy-
ranoside 3b in 76% (Scheme 1). In continuation of this, we also
explored the utility of the current protocol to the other glycosyl
1,2-orthoesters, such as glucosyl (4), galactosyl (6) and lactosyl
(8) 1,2-orthoesters (prepared, respectively, in 76%, 65%, and 63%
yield from corresponding aldoses) to obtain corresponding glyco-
sides 5a, 5b, 7a, 7b, 9a, and 9b from aglycones 2a and 2b in good
yields (Scheme 1). Glycopolymers can be obtained from these acry-
lates easily by free radical polymerization and then exhaustive
saponification of all benzoyl groups would be necessary in order
to get the polyhydroxy glycopolymers. However, orthogonal
deprotection of benzoates in the presence of acrylate esters poses
a formidable task. Thus, hydroxylethyl acrylamides were consid-
ered to be superior as they would enable preparation of glycopoly-
mers with acrylamide backbone and later facilitate easy
saponification of benzoates to get water soluble polyacrylamides.
Accordingly, per-O-benzoylated mannose 1,2-orthoester (1)
was allowed to react with commercially available hydroxyethyl
acrylamide 10a and hydroxyethyl methacrylamide 10b in the pres-
ence of 7 mol % of AuBr3. Surprisingly, a single product identified as
per-O-benzoylated hydroxyethyl acrylamide 1,2-orthoester (11a)
was isolated which was subsequently converted to the required
mannose-hydroxy ethyl acrylamide conjugate 12a by reacting
with TMSOTf in CH2Cl2 at room temperature in 69% over two steps.
A similar attempt with the hydroxyethyl methacrylamide also gave
first the orthoester (11b) which could then be converted to the
mannopyranoside 12b with an overall yield of 68%. The general
applicability of this methodology has been gauged with the other
orthoesters 4, 6, and 8 to obtain corresponding acrylamides 13a,
13b, 14a, 14b, 15a, and 15b in very good yields (Scheme 2).12 A sin-
gle step conversion of orthoester 1 to 12a, 12b in the presence of
TMSOTf was found to give only a small quantity of desired product
(10%) and the major product was observed to be the propargyl
Reagent
Method 2:
Orthogonal
=
Functional Groups
Glycopolymer
Reagent
Reagent
Polymer
Glycopolymer
Figure 1. Strategies for glycopolymer synthesis.
Alternatively, glycopolymers can also be synthesized in a two
step manner; first polymers are synthesized with a functional
group that can then be used to stick a sugar monomer with an
orthogonal functional group ( Fig. 1). For example, Haddleton’s
group has successfully synthesized alkynated polymers and then
attached sugar moieties through a CuAAC (or ‘click’) reaction.9
Along with the inherent merits of the post-polymer synthesis
grafting method, the ambiguous number of attached sugar resi-
dues which is often difficult to estimate and the distribution of gly-
cosides along the polymeric backbone are the limitations. The key
in both of these approaches is the easy access to sugar-monomer
glycosides.7 The existing methods for the preparation of sugar-
monomers suffer from one or more of the drawbacks such as harsh
reactions, high temperatures, tedious work-up, laborious purifica-
tion procedures, and many a time the reaction conditions interfere
with the functional groups present on the required aglycone.7
In this context, our recently identified methodology for
1,2-trans diastereoselective saccharides and glycosides from corre-
sponding propargyl 1,2-orthoesters using AuBr3 would be ideal as
the glycosyl donor activation procedure tolerates a wide range of
functional groups.10 Some of the major advantages of glycosylation
by means of propargyl 1,2-orthoesters are (i) the reaction is high
yielding and stereoselective, (ii) the glycosyl donor is stable and
can be easily accessed in two steps from the aldose and (iii) the
glycosyl donor activation by AuBr3 tolerates the presence of
alkenes, ethers, esters, etc. Thus we envisioned that the AuBr3 cat-
alyzed glycosylation of versatile and polymerizable aglycones, such
as hydroxyethyl acrylates/acrylamides and hydroxy-amino acids
could be possible as the reagents used for glycosylation do not
react with alkenes.10
2,3,4,6-tetra-O-benzoyl a-D
-mannopyanoside10a (70%) may be be-
cause of the strong Lewis and Bronsted acidity of TMSOTf. Hence
preparation of the hybrids through gold catalyzed glycosidation
is advantageous.
Glycosides of acrylate/acrylamide are excellent scaffolds for
attaching cysteine or any mercaptan per se. BocCys(SH)OMe (16)
was considered as a model substrate for the ‘thiol-ene click’ reac-
tion.13 For example, cysteine residue 16 smoothly reacted with
acrylate (3a) or acrylamide (12a) in the presence of Et3N in EtOH
at room temperature to give Michael addition products 17a and
17b, respectively (Scheme 3).14,12 Similarly, lactose derived acry-
late 9a gave the corresponding ‘thio-click’ product in 85% yield
whereas galactose-methacrylate 7b resulted in the isolation of
thiolate addition product as a 1:1 diastereomeric mixture at the
newly generated chiral center (Scheme 4).
2. Results and discussion
The most commonly studied glycopolymers have been the
water soluble poly(vinylsachharides) which are typically glyco-
polymers with a pendant carbohydrate on a acrylate, acrylamide,
polypeptide, or polystyrene backbone.11 The first three glycopoly-
mers mentioned above are typically synthesized by vinyl-type
free-radical polymerization of well-defined saccharide-based
monomers. The monomers are in turn prepared by coupling an
unsaturated component to a carbohydrate derivative through an
ether, ester, or amido linkage. A key challenge in this area has been
the development of a general methodology that affords synthesis
of such monomeric materials in high yields.7
3. Synthesis of glycopolymers
Several methodologies have been developed for polymerization
of carbohydrate based acrylamido monomers. These include both
conventional free radical and stable free radical (SFRP) polymeriza-
tion methods.15 In an attempt to show that the monomers synthe-
sized by our methodology can also be polymerized, we attempted
the oligomerization of per-O-benzoylated glucose acrylamide
monomer using AIBN as the initiator and 2-aminoethanethiol
hydrochloride as the CTA in DMF.16 The resulting polymer was
characterized by both NMR and GPC analysis. The Mn was deter-
mined to be 5600 Da while the PDI was found to be 1.08.
Mannose-derived 1,2-orthoester (1)10 prepared in three steps
from D-mannose in an overall yield of 70% and commercially avail-
Since, 2-aminoethanethiol hydrochloride was used as the CTA,
the polymer chains had an amino end group which can be further
able hydroxyethyl acrylate (2a) were treated with 7 mol % of AuBr3
in CH2Cl2/4 Å MS powder at room temperature for 10 h to obtain

S. A. Thadke et al. / Carbohydrate Research 346 (2011) 1511–1518
1513
OBz
OBz
Ph
O
O
O
O
BzO
HO
R1
BzO
a
+
BzO
BzO
O
O
O
O
O
O
R1
BzO
O
1
2a
3a
R1 = H (10h, 78%)
R1 = H
2b R1 = CH3
3b R1 = CH3 (8h, 76%)
OBz
OBz
O
O
O
BzO
BzO
a
a
+
+
BzO
BzO
2a 2b
O
or
R1
O O
OBz
R1 = H (4h, 73%)
5b R1 = CH3 (1h, 71%)
O
Ph
4
5a
OBz
BzO
OBz
O
BzO
O
O
BzO
2a or 2b
2a or 2b
O
R1
O O
BzO
7a
O
OBz
R1 = H (12h, 69%)
7b R1 = CH3 (14h, 71%)
6
8
O
Ph
OBz
O
BzO
BzO
OBz
O
OBz
O
BzO
BzO
OBz
O
a
O
O
+
BzO
O
O
R1
OBz
O O
BzO
O
OBz
OBz
9a
R1 = H (10h, 77%)
O
Ph
9b R1 = CH3 (8h, 79%)
Scheme 1. Synthesis of sugar-acrylate monomers. Reagents: (a) AuBr3, CH2Cl2, 4 Å MS, rt.
Ph
O
O
OBz
OBz
BzO
BzO
O
O
O
BzO
BzO
Ph
O
BzO
O
1
O
BzO
BzO
R1
O
O
a
NH
b
N
H
O
+
O
BzO
12a R1 = H (10h, 69%)
O
HO
R1
12b
R1 = CH3 (14h, 68%)
N
H
R1
11a R1 = H
11b
10a R1 = H
OBz
R
1 = CH3
10b
R
1 = CH3
O
BzO
O
OBz
O
BzO
OBz
BzO
BzO
a,b
NH
+
10a or 10b
O O
Ph
OBz
O
4
13a R1 = H (6h, 74%)
O
R1
13b R1 = CH3 (6h, 70%)
BzO
BzO
OBz
O
BzO
BzO
O
O
a,b
10a
10b
or
+
O
R1
O O
N
H
OBz
R1 = H (15h, 69%)
6
O
Ph
14a
14b
R1 = CH3 (14h, 73%)
OBz
O
BzO
BzO
OBz
OBz
O
BzO
OBz
O
O
O
a,b
+
10a or 10b
O
BzO
OBz
O
O
R1
BzO
O O
Ph
BzO
N
OBz
OBz
H
8
O
15a
15b
R1 = H (14h, 70%)
R1 = CH3 (16h, 72%)
Scheme 2. Synthesis of sugar-acrylamide monomers. Reagents: (a) AuBr3, CH2Cl2, 4 Å MS, rt; (b) TMSOTf, CH2Cl2, rt.
modified using amine reactive compounds. The per-O-benzoate
groups of the resulting oligomer were removed under Zemplén
conditions using sodium methoxide to afford the polymer contain-
ing free hydroxyl groups of the carbohydrate.10 To be able to prove
that the biofunctionality of the glucose moieties is still active and
not lost during the polymerization process, the ligand-lectin bind-
ing ability of the glycopolymer was tested by specific binding using
Concanavalin A lectins interaction with a-D
-glucose moieties.4 The

1514
S. A. Thadke et al. / Carbohydrate Research 346 (2011) 1511–1518
OBz
OBz
time and the completion of the reaction is judged by TLC analysis.
The reaction mixture was filtered through Celite and the filtrate
was concentrated in vacuo to obtain a crude residue which was
purified by conventional silica gel column chromatography using
ethyl acetate–petroleum ether as mobile phase.
O
BzO
BzO
HS
BocHN
O
3a
or
a
+
O
12a
X
CO2Me
17a
X = O (81%)
R
16
16
17b
X = NH (90%)
S
OBz
BzO
BzO
5.2. General procedure for the synthesis of sugar-acrylamide
monomers
OBz
O
O
O
O
OBz
a
O
BzO
9a
7b
+
O
OBz
(85%)
To a solution of glycosyl donor10 1 (0.635 gm, 1 mmol), glycosyl
acceptor 10b (0.142 g 1.1 mmol) and 4 Å molecular sieves powder
(100 mg) in anhydrous CH2Cl2 (10 mL) was added AuBr3 (0.031 g,
0.07 mmol) under argon atmosphere at room temperature. The
reaction mixture was stirred at room temperature for the specified
time and the completion of the reaction is judged by TLC analysis.
The reaction mixture was filtered through Celite and the filtrate
was concentrated in vacuo to obtain a crude residue which was
purified by conventional silica gel column chromatography using
ethyl acetate–petroleum ether as mobile phase to obtain com-
pound 11b. Further, compound 11b was dissolved in dry dichloro-
R
S
17c
OBz
O
BzO
BzO
O
O
a
O
R =
16
+
CO2Me
OBz
BocHN
R
17d
S
(82%)
Scheme 3. Acrylate/acrylamide monomers for thiolate addition. Reagents: (a) Et3N,
EtOH, 8 h, rt.
rate of aggregation of the polymer with conA was monitored at
490 nm, where no absorbance of either the polymer or con-A is
observed. This turbidity assay measures the changes in absorbance
at a wavelength of 490 nm using UV–vis spectroscopy. The binding
of the multivalent polymer to Con A forms a gel network with con-
comitant increase in size that causes significant scattering, thus
leading to a turbid solution. The turbidity increases with conjuga-
tion time and plateaus after 3 min. Similar multivalent characteris-
tics showed by the polyvalent glycopolymers were also observed
earlier by Kiessling and co-workers.17
methane (10 mL) and trifluoromethanesulphonate (5 lL) was
added and the reaction mixture was stirred for 5 min at room tem-
perature and diluted with dichloromethane (10 mL) and water
(10 mL). The organic layer was separated and concentrated in va-
cuo to obtain a crude residue which was purified by conventional
silica gel column chromatography using ethyl acetate-petroleum
ether as mobile phase.
5.3. Procedure for the thiolate addition
4. Conclusions
Acrylate monomer 3a (0.200 g, 0.29 mmol) and cysteine deriva-
tive 16 (0.166 g, 0.72 mmol) were dissolved in ethanol (1 mL) and
Et3N (0.5 mL) under argon atmosphere at room temperature. The
reaction mixture was stirred at room temperature for the specified
time and the completion of the reaction is judged by TLC analysis.
The reaction mixture was concentrated in vacuo to obtain a crude
residue which was purified by conventional silica gel column chro-
matography using ethyl acetate–petroleum ether as mobile phase
to obtain thiolate addition product 17a (0.21 g, 82%).
In conclusion, a new synthesis methodology was identified for
the easy synthesis of sugar-acrylate/acrylamide from stable glyco-
syl 1,2-orthoesters taking the cue from gold catalyzed glycosyla-
tions. Thiolate Michael addition onto sugar-acrylate/acrylamide
was also studied that would serve as an alternate synthesis for
amino acid glycoconjugates as well as a strategy for the glycosyla-
tion of cysteine containing proteins. Furthermore, we showed that
the sugar monomers prepared in this study are good for carrying
out polymerization. We anticipate that this simple, easy, scalable,
and stereoselective methodology for the sugar monomers would
catalyze the easy preparation of glycopolymers.
5.4. Procedure for the synthesis of glycopolymer 31
The per-O-benzoylated monomer (13a) (400 mg, 641.3
lmol),
2-aminoethanethiol hydrochloride (3.64 mg, 32.06 mol) and
l
AIBN (4% by weight of the monomer) were dissolved under N2 in
anhydrous DMF (0.4 mL) in a Schelnk tube with side arm, sub-
jected to three freeze–pump–thaw cycles, cannulated into the
polymerization flask, and magnetically stirred at 60 °C for 72 h.
The reaction mixture was cooled, concentrated under diminished
pressure, and poured into a large excess of Et2O (100 mL/g of oligo-
mer). The oligomer 30 was filtered and further purified through
two dissolution (in tetrahydrofuran)/precipitation cycles (in Et2O)
until the disappearance of the residual monomers (13a) as moni-
tored by TLC. The polymer was characterized by GPC in chloroform
5. Experimental section
5.1. General procedure for the synthesis of sugar-acrylate
monomers
To a solution of glycosyl donor 1 (0.635 g, 1 mmol), glycosyl
acceptor 2b (0.143 g, 1.1 mmol) and 4 Å molecular sieves powder
(100 mg) in anhydrous CH2Cl2 (10 mL) was added AuBr3 (0.031 g,
0.07 mmol) under argon atmosphere at room temperature. The
reaction mixture was stirred at room temperature for the specified
OR
NH2.HCl
S
O
HS(CH2)2NH2.HCl
RO
RO
O
H
13a
n
AIBN, DMF, 60oC, 82%
OR
N
H
O
18
R = COPh
NaOCH3
CH3OH, rt
39
42
45
48
19 R =H
Elution time (min)
Scheme 4. Free radical polymerization of gluco-acrylamide (inset: GPC of the resulting polymer).

S. A. Thadke et al. / Carbohydrate Research 346 (2011) 1511–1518
1515
and by NMR spectral analysis. A very narrow molecular weight
6.5. 2-(Acryloyloxy)ethyl 2,3,4,6-tetra-O-benzoyl b-
D-
distribution (MWD) was obtained from Gel Permeation
Chromatography (Mw/Mn = 1.08). Yield: 72%. Subsequently, oligo-
mer 30 was redissolved in 10 mL of anhydrous MeOH, freshly
prepared sodium methoxide (1 mL) was added to the reaction mix-
ture, and stirred for 4 h at room temperature. After 4 h the reaction
mixture was quenched with Amberlite IR-120 resin, filtered, and
concentrated in vacuo to obtain the glycopolymer 31.
galactopyranoside (7a)
½
a 2D5
ꢀ
+76.0 (c 1.1, CHCl3); IR (CHCl3): 3072, 1726, 1603, 1267,
1111, 765 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d 3.89 (m, 1H),
;
4.13–4.51 (m, 4H), 4.71 (dd, 1H, J 5.5, 10.1 Hz), 4.94 (dd, 1H, J
0.7, 7.9 Hz), 5.58 (dd, 1H, J 1.7, 10.4 Hz), 5.65 (ddd, 1H, J 0.9, 3.5,
10.5 Hz), 5.80 (m, 2H), 6.03 (d, 1H, J 3.3 Hz), 6.19 (dd, 1H, J 1.7,
17.2 Hz), 6.44 (dd, 1H, J 1.7, 17.2 Hz), 7.12–7.68 (m, 12H), 7.73–
8.15 (m, 8H); 13C NMR (CDCl3, 50.32 MHz): d 61.9, 63.0, 67.5,
68.0, 69.5, 71.3, 71.5, 101.4, 127.6, 127.9–130.0, 130.8, 133.1,
133.2, 133.2, 133.5, 165.1, 165.4, 165.5, 165.7, 165.9; HRMS (MAL-
DI-TOF): m/z: calcd for [C39H34O12+Na]+: 717.1948, found:
717.1883.
6. Compound characterization data
6.1. 2-(Acryloyloxy)ethyl 2,3,4,6-tetra-O-benzoyl a-D-
mannopyranoside (3a)
½
a 2D5
ꢀ
ꢁ52.5 (c 1.4, CHCl3); IR (CHCl3): 3057, 2976, 1726, 1603,
1264, 1215, 1109, 771 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d
;
6.6. 2-(Methacryloyloxy)ethyl 2,3,4,6-tetra-O-benzoyl b-D-
3.83–4.05 (m, 2H), 4.39–4.78 (m, 5H), 5.17 (d, 1H, J 1.8 Hz), 5.75
(dd, 1H, J 1.8, 3.3 Hz), 5.87 (dd, 1H, J 1.6, 10.4 Hz), 5.93 (dd, 1H, J
3.3, 10.3 Hz), 6.13 (t, 1H, J 10.3 Hz), 6.21 (dd, 1H, J 10.3, 17.3 Hz),
6.50 (dd, 1H, J 1.6, 17.3 Hz), 7.20–7.66 (m, 12H), 7.78–8.15 (m,
8H); 13C NMR (CDCl3, 50.32 MHz): d 62.8, 63.1, 66.1, 66.8, 69.0,
69.9, 70.2, 97.6, 127.9, 128.3–129.8, 131.4, 133.1, 133.2, 133.4,
133.5, 165.3, 165.4, 165.4, 165.9, 166.1; HRMS (MALDI-TOF): m/
z: calcd for [C39H34O12+Na]+: 717.1948, found: 717.1938.
galactopyranoside (7b)
½
a 2D5
ꢀ
+78.5 (c 1.0, CHCl3); IR (CHCl3): 3065, 2976, 1728, 1602,
1267, 1215, 756 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d 1.74 (s,
;
3H), 3.92 (qd, 1H, J 3.9, 6.8, 11.1 Hz), 4.11–4.49 (m, 5H), 4.69 (dd,
1H, J 4.7, 10.5 Hz), 4.03 (d, 1H, J 7.8 Hz), 5.33 (quintent, 1H, J 1.6,
3.1 Hz), 5.63 (dd, 1H, J 3.5, 10.5 Hz), 5.78–6.04 (m, 3H), 7.15–7.68
(m, 12H), 7.75–8.18 (m, 8H); 13C NMR (CDCl3, 50.32 MHz): d
18.0, 61.9, 63.3, 67.4, 68.0, 69.5, 71.3, 71.6, 101.3, 125.7, 128.1–
129.9, 133.1, 133.2, 133.2, 133.5, 135.6, 165.1, 165.5, 165.5,
166.0, 167.0; HRMS (MALDI-TOF): m/z: calcd for [C40H36O12+Na]+:
731.2104, found: 731.2230.
6.2. 2-(Methacryloyloxy)ethyl 2,3,4,6-tetra-O-benzoyl a-D-
mannopyranoside (3b)
½
a 2D5
ꢀ
ꢁ54.1 (c 1.3, CHCl3); IR (CHCl3): 3064, 2976, 1728, 1603,
1265, 1215, 1109, 770 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d
;
6.7. 2-(Acryloyloxy)ethyl 2,3,6-tri-O-benzoyl-4-O-(2,3,4,6-tetra-
1.99 (dd, 3H, J 1.0, 1.5 Hz), 3.83–4.16 (m, 2H), 4.38–4.75 (m, 5H),
5.17 (d, 1H, J 1.8 Hz), 5.62 (quintet, 1H, J 1.5, 3.2 Hz), 5.73 (dd,
1H, J 1.8, 3.3 Hz), 5.93 (dd, 1H, J 3.3, 10.1 Hz), 6.07–6.23 (m, 2H),
7.21–7.68 (m, 12H), 7.76–8.15 (m, 8H); 13C NMR (CDCl3,
50.32 MHz): d 18.3, 62.6, 63.1, 65.9, 66.7, 68.8, 69.8, 70.1, 97.4,
126.0, 128.1–129.8, 133.0, 133.1, 133.4, 133.4, 135.9, 165.2,
165.3, 165.3, 166.0, 167.0; HRMS (MALDI-TOF): m/z: calcd for
[C40H36O12+Na]+: 731.2104, found: 731.2135.
O-benzoyl-b-D-galactopyranosyl)-b-D-glucopyranoside (9a)
½
a 2D5
ꢀ
+48.4 (c 1.1, CHCl3); IR (CHCl3): 3064, 2976, 1730, 1603,
1215, 1095, 769 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d 3.56–3.99
;
(m, 6H), 4.05–4.29 (m, 3H), 4.41 (dd, 1H, J 3.7, 12.3 Hz), 4.53 (dd,
1H, J 1.7, 12.3 Hz), 4.74 (ABq, 2H, J 7.9 Hz), 5.25–5.51 (m, 3H),
5.53–5.84 (m, 4H), 6.06 (dd, 1H, J 1.6, 17.0 Hz), 7.00–7.53 (m,
21H), 7.55–8.01 (m, 14H); 13C NMR (CDCl3, 50.32 MHz): d 60.9,
62.2, 63.0, 67.4, 67.4, 69.8, 71.3, 71.5, 71.7, 72.7, 73.0, 75.8,
100.9, 101.0, 127.6, 128.0–129.9, 130.8, 133.1, 133.2, 133.3,
133.3, 133.3, 133.4, 133.5, 164.7, 165.0, 165.1, 165.3, 165.3,
165.5, 165.7, 165.8; HRMS (MALDI-TOF): m/z: calcd for
[C66H56O20+Na]+: 1191.3263, found: 1191.3123.
6.3. 2-(Acryloyloxy)ethyl 2,3,4,6-tetra-O-benzoyl b-D-
glucopyranoside (5a)
½
a 2D5
ꢀ
+18.8 (c 1.2, CHCl3); IR (CHCl3): 3064, 2974, 1732, 1602,
1248, 1215, 1105, 758 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d
3.81–3.93 (m, 1H), 4.04–4.35 (m, 4H), 4.49 (dd, 1H, 5.1,
;
J
6.8. 2-(Methacryloyloxy)ethyl 2,3,6-tri-O-benzoyl-4-O-(2,3,4,6-
12.1 Hz), 4.65 (dd, 1H, J 3.3, 12.1 Hz), 4.92 (d, 1H, J 7.8 Hz), 5.50–
5.98 (m, 5H), 6.20 (dd, 1H, J 1.7, 17.2 Hz), 7.21–7.63 (m, 12H),
7.78–8.09 (m, 8H); 13C NMR (CDCl3, 50.32 MHz): d 63.0, 63.0,
67.5, 69.6, 71.6, 72.3, 72.7, 101.1, 127.7, 128.0–129.8, 130.9,
133.1, 133.2, 133.2, 133.4, 165.0, 165.1, 165.8, 165.8, 166.1; HRMS
(MALDI-TOF): m/z: calcd for [C39H34O12+Na]+: 717.1948, found:
717.1981.
tetra-O-benzoyl-b-D-galactopyranosyl)-b-D-glucopyranoside (9b)
½
a 2D5
ꢀ
+49.2 (c 1.3, CHCl3); IR (CHCl3): 3064, 2976, 1730, 1603,
1452, 1269, 1215, 1096, 758 cmꢁ1 1H NMR (CDCl3, 200.13 MHz):
;
d 1.71 (s, 3H), 3.65–4.08 (m, 6H), 4.10–4.38 (m, 3H), 4.48 (dd, 1H,
J 3.9, 12.4 Hz), 4.60 (dd, 1H, J 1.3, 12.4 Hz,), 4.82 (ABq, 2H, J
7.9 Hz), 5.28 (quintet, 1H, J 1.6, 3.2 Hz), 5.37 (dd, 1H, J 3.3,
10.3 Hz), 5.48 (dd, 1H, J 7.9, 9.9 Hz), 5.66–5.87 (m, 4H), 7.09–7.64
(m, 21H), 7.69–8.05 (m, 14H); 13C NMR (CDCl3, 50.32 MHz): d
18.0, 61.0, 62.2, 63.2, 67.4, 67.5, 69.8, 71.4, 71.5, 71.7, 72.8, 73.0,
75.9, 100.9, 101.0, 125.7, 128.1–130.0, 133.2, 133.3, 133.4, 133.4,
133.4, 133.4, 133.5, 135.6, 164.8, 165.1, 165.2, 165.4, 165.4,
165.5, 165.8, 167.0; HRMS (MALDI-TOF): m/z: calcd for
[C67H58O20+Na]+: 1205.3419, found: 1205.3211.
6.4. 2-(Methacryloyloxy)ethyl 2,3,4,6-tetra-O-benzoyl b-D-
glucopyranoside (5b)
½
a 2D5
ꢀ
+27.8 (c 1.2, CHCl3); IR (CHCl3): 3069, 2976, 1730, 1603,
1265, 1215, 1106, 769 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d
;
1.74 (dd, 3H, J 1.0, 1.4 Hz), 3.85 (m, 1H), 4.04–4.36 (m, 4H), 4.49
(dd, 1H, J 4.5, 12.2 Hz), 4.65 (dd, 1H, J 3.2, 12.2 Hz), 4.92 (d, 1H, J
7.8 Hz), 5.33 (m, 1H), 5.50–5.98 (m, 4H), 7.22–7.60 (m, 12H),
7.78–8.10 (m, 8H); 13C NMR (CDCl3, 50.32 MHz): d 18.0, 63.0,
63.2, 67.4, 69.6, 71.6, 72.3, 72.8, 101.0, 125.8, 128.1–130.0, 133.1,
133.2, 133.3, 133.4, 135.7, 165.0, 165.2, 165.8, 166.1, 167.1; HRMS
(MALDI-TOF): m/z: calcd for [C40H36O12+Na]+: 731.2104, found:
731.2171.
6.9. 3,4,6-Tri-O-benzoyl-1,2-O-[(2-acrylamidoethoxy)
phenylmethylene]-b-D-mannopyrano-side (11a)
½
a 2D5
ꢀ
ꢁ73.2 (c 1.2, CHCl3); IR (CHCl3): 3439, 3393, 3323, 3065,
2955, 1724, 1664, 1524, 1450, 1269, 1076, 761 cmꢁ1 1H NMR
(CDCl3, 200.13 MHz): d 3.42–3.63 (m, 4H), 4.08 (ddd, 1H, J 3.3,
;

1516
S. A. Thadke et al. / Carbohydrate Research 346 (2011) 1511–1518
4.4, 7.7 Hz), 4.33 (dd, 1H, J 4.6, 12.2 Hz), 4.53 (dd, 1H, J 3.2,
12.2 Hz), 5.08 (dd, 1H, J 2.9, 3.2 Hz), 5.59 (d, 1H, J 1.8, 10.0 Hz),
5.63 (dd, 1H, J 3.6, 10.4 Hz), 5.81 (d, 1H, J 4.8 Hz), 5.85 (d, 1H, J
9.5 Hz), 5.97 (m, 1H), 6.08 (d, 1H, J 10.0 Hz), 6.24 (d, 1H, J 1.8,
16.9 Hz), 7.22–7.70 (m, 14H), 7.85–8.06 (m, 6H); 13C NMR (CDCl3,
50.32 MHz): d 39.0, 62.8, 62.9, 66.2, 71.1, 71.8, 76.4, 97.8, 122.9,
126.2, 126.5, 128.1–129.7, 129.9, 130.5, 132.9, 133.4, 133.5,
136.3, 165.1, 165.4, 165.9, 165.9; HRMS (MALDI-TOF): m/z: calcd
for [C39H35NO11+Na]+: 716.2108, found: 716.2220.
5.66–6.00 (m, 3H), 6.14 (dd, 1H, J 1.5, 16.9 Hz), 6.13 (s, 1H),
7.20–7.63 (m, 12H), 7.80–8.09 (m, 8H); 13C NMR (CDCl3,
50.32 MHz): d 39.1, 62.7, 69.3, 69.3, 71.9, 72.4, 72.6. 101.4, 126.3,
128.2–129.8, 130.4, 133.3, 133.3, 133.5, 133.5, 165.1, 165.2,
165.4, 165.7, 166.1; HRMS (MALDI-TOF): m/z: calcd for
[C39H35NO11+Na]+: 716.2108, found: 716.2194.
6.14. 2-Methacrylamido ethyl 2,3,4,6-tetra-O-benzoyl-b-D-
glucopyranoside (13b)
6.10. 3,4,6-Tri-O-benzoyl-1,2-O-[(2-
methacrylamidoethoxy)phenylmethylene]-b-
½
a 2D5
ꢀ
+29.1 (c 1.1, CHCl3); IR (CHCl3): 3391, 3310, 3064, 2957,
D-
1728, 1603, 1451, 1215, 1113, 1026, 756 cmꢁ1 1H NMR (CDCl3,
;
mannopyranoside (11b)
200.13 MHz): d 1.74 (s, 3H), 3.32–3.68 (m, 2H), 3.77 (ddd, 1H, J
3.7, 7.5, 10.2 Hz), 3.96 (ddd, 1H, J 3.6, 5.6, 9.4 Hz), 4.19 (ddd, 1H,
J 3.0, 5.1, 8.2 Hz), 4.49 (dd, 1H, J 5.2, 12.2 Hz), 4.66 (dd, 1H, J 2.9,
12.2 Hz), 4.89 (d, 1H, J 7.9 Hz), 5.10 (quintet, 1H, J 1.6, 2.9 Hz),
5.50 (s, 1H), 5.55 (dd, 1H, J 7.9, 9.7 Hz), 5.70 (t, 1H, J 9.7 Hz), 5.94
(t, 1H, J 9.7 Hz), 6.20 (t, 1H, J 5.3 Hz), 7.20–7.65 (m, 12H), 7.78–
8.08 (m, 8H); 13C NMR (CDCl3, 50.32 MHz): d 18.2, 39.1, 62.9,
69.0, 69.4, 71.9, 72.3, 72.6, 101.2, 119.5, 128.2–129.8, 133.2,
133.2, 133.4, 133.4, 139.5, 165.1, 165.1, 165.7, 166.0, 168.2; HRMS
(MALDI-TOF): m/z: calcd for [C40H37NO11+Na]+: 730.2264,
found:730.2349.
½
a 2D5
ꢀ
ꢁ77.2 (c 1.1, CHCl3); IR (CHCl3): 3443, 3412, 3065, 2928,
1728, 1672, 1518, 1452, 1269, 1093, 758 cmꢁ1
;
1H NMR (CDCl3,
200.13 MHz): d 1.94 (s, 3H), 3.30 (m, 2H), 3.92–4.29 (m, 3H),
4.50 (dt, 2H, J 4.0, 11.9 Hz), 4.77 (dd, 1H, J 2.8, 12.2 Hz), 5.26 (t,
1H, J 1.4 Hz), 5.58 (d, 1H, J 2.4 Hz), 5.63 (dd, 1H, J 4.2, 9.9 Hz),
5.72 (br s, 1H), 6.11 (t, 1H, J 9.8 Hz), 6.35 (t, 1H, J 5.1 Hz), 7.22–
7.65 (m, 14H), 7.89–8.15 (m, 6H); 13C NMR (CDCl3, 50.32 MHz): d
18.6, 39.2, 62.2, 62.3, 66.1, 71.2, 71.8, 75.7, 95.7, 119.3, 123.5,
125.5, 128.2–130.0, 133.4, 133.5, 133.6, 137.8, 140.0, 165.1,
165.8, 166.0, 168.3; HRMS (MALDI-TOF): m/z: calcd for
[C40H37NO11+Na]+: 730.2264, found: 730.2245.
6.15. 2-Acrylamido ethyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranoside (14a)
6.11. 2-Acrylamido ethyl 2,3,4,6-tetra-O-benzoyl-a-D-
mannopyranoside (12a)
½
a 2D5
ꢀ
+79.7 (c 1.1, CHCl3); IR (CHCl3): 3392, 3314, 3067, 2976,
1728, 1603, 1217, 1113, 772 cmꢁ1 1H NMR (CDCl3, 200.13 MHz):
;
½
a 2D5
ꢀ
ꢁ58.0 (c 1.2, CHCl3); IR (CHCl3): 3393, 3308, 3064, 2932,
d 3.33–3.86 (m, 3H), 4.04 (ddd, 1H, J 3.7, 5.4, 8.9 Hz), 4.41 (m,
2H), 4.68 (dd, 1H, J 6.2, 10.6 Hz), 4.86 (d, 1H, J 7.7 Hz), 5.42 (dd,
1H, J 1.4, 10.6 Hz), 5.60–5.80 (m, 3H), 5.98–6.19 (m, 3H), 7.17–
7.78 (m, 12H), 7.75–8.14 (m, 8H); 13C NMR (CDCl3, 50.32 MHz): d
38.9, 62.0, 68.0, 69.1, 69.8, 71.2, 71.4. 101.6, 126.2, 128.2–130.0,
130.3, 133.3, 133.3, 133.5, 133.6, 165.4, 165.4, 165.4, 165.4,
166.0; HRMS (MALDI-TOF): m/z: calcd for [C39H35NO11+Na]+:
716.2108, found: 716.2123.
1732, 1628, 1452, 1267, 1109, 1070, 756 cmꢁ1 1H NMR (CDCl3,
;
200.13 MHz): d 3.55–3.89 (m, 3H), 3.97 (m, 1H), 4.40–4.56 (m,
2H), 4.70 (m, 1H), 5.12 (d, 1H, J 1.6 Hz), 5.69 (dd, 1H, J 2.4,
9.5 Hz), 5.74 (dd, 1H, J 1.8, 3.3 Hz), 5.91 (dd, 1H, J 3.3, 10.1 Hz),
6.12 (t, 1H, J 9.9 Hz), 6.28 (d, 1H, J 9.5 Hz), 6.34 (d, 1H, J 2.3 Hz),
6.45 (m, 1H), 7.20–7.65 (m, 12H), 7.70–8.14 (m, 8H); 13C NMR
(CDCl3, 50.32 MHz): d 39.2, 62.8, 66.8, 67.6, 69.0, 70.0, 70.2, 97.8,
126.9, 128.2–129.8, 130.6, 133.1, 133.3, 133.5, 133.5, 165.4,
165.4, 165.6, 165.7, 166.1; HRMS (MALDI-TOF): m/z: calcd for
[C39H35NO11+Na]+: 716.2108, found:716.2220.
6.16. 2-Methacrylamido ethyl 2,3,4,6-tetra-O-benzoyl-b-D-
galactopyranoside (14b)
6.12. 2-Methacrylamido ethyl 2,3,4,6-tetra-O-benzoyl-
mannopyranoside (12b)
a-
D-
½
a 2D5
ꢀ
+81.3 (c 1.1, CHCl3); IR (CHCl3): 3393, 3310, 3071, 2945,
1728, 1603, 1457, 1215, 1113, 756 cmꢁ1 1H NMR (CDCl3,
;
200.13 MHz): d 1.75 (s, 3H), 3.35–3.85 (m, 3H), 4.03 (ddd, 1H, J
3.7, 5.8, 9.4 Hz), 4.41 (m, 2H), 4.67 (dd, 1H, J 6.1, 10.5 Hz), 4.88
(d, 1H, J 7.9 Hz), 5.11 (quintet, 1H, J 1.4, 2.9 Hz), 5.51 (s, 1H), 5.66
(dd, 1H, J 3.3, 10.3 Hz), 5.82 (dd, 1H, J 7.7, 10.5 Hz), 6.02 (d, 1H, J
3.3 Hz), 6.25 (t, 1H, J 5.4 Hz), 7.18–7.69 (m, 12H), 7.78–8.15 (m,
8H); 13C NMR (CDCl3, 50.32 MHz): d 18.2, 39.1, 62.0, 68.0, 68.8,
69.8, 71.4, 71.4, 101.4, 119.5, 128.2–129.9, 133.3, 133.3, 133.4,
133.6, 139.5, 165.3, 165.4, 165.4, 165.4, 168.4; HRMS (MALDI-
TOF): m/z: calcd for [C40H37NO11+Na]+: 730.2264, found:730.2194.
½
a 2D5
ꢀ
ꢁ53.5 (c 0.9, CHCl3); IR (CHCl3): 3480, 3439, 3086, 2930,
1730, 1662, 1452, 1267, 1109, 1068, 758 cmꢁ1 1H NMR (CDCl3,
;
400.13 MHz): d 2.0 (s, 3H), 3.58–3.80 (m, 3H), 4.10 (m, 1H), 4.44
(ddd, 1H, J 2.7, 4.3, 7.1 Hz), 4.52 (dd, 1H, J 4.6, 12.2 Hz), 4.71 (dd,
1H, J 2.5, 12.2 Hz), 5.15 (d, 1H, J 1.4 Hz), 5.41 (t, 1H, J 1.4 Hz),
5.74 (dd, 1H, J 1.7, 3.2 Hz), 5.81 (s, 1H), 5.93 (dd, 1H, J 3.3,
10.2 Hz), 6.12 (t, 1H, J 10.1 Hz), 6.41 (t, 1H, J 5.3 Hz), 7.25–7.68
(m, 12H), 7.83–8.12 (m, 8H); 13C NMR (CDCl3, 100.61 MHz): d
18.7, 39.3, 62.8, 66.8, 67.4, 69.1, 69.9, 70.2, 97.7, 120.0, 128.3–
129.9, 133.1, 133.3, 133.5, 133.6, 139.8, 165.4, 165.4, 165.6,
166.1, 168.5; HRMS (MALDI-TOF): m/z: calcd for [C40H37NO11+-
Na]+: 730.2264, found: 730.2245.
6.17. 2-(Acrylamido)ethyl 2,3,6-tri-O-benzoyl-4-O-(2,3,4,6-tetra-
O-benzoyl-b-D-galactopyranosyl)-b-D-glucopyranoside (15a)
½
a 2D5
ꢀ
+46.2 (c 1.1, CHCl3); IR (CHCl3): 3390, 3315, 3066, 2976,
6.13. 2-Acrylamido ethyl 2,3,4,6-tetra-O-benzoyl-b-
D
-
1730, 1603, 1452, 1269, 1215, 756 cmꢁ1 1H NMR (CDCl3,
;
glucopyranoside (13a)
200.13 MHz): d 3.25–4.06 (m, 8H), 4.27 (t, 1H, J 9.4 Hz), 4.49 (dd,
1H, J 3.8, 12.2 Hz), 4.66 (dd, 1H, J 1.3, 10.2 Hz), 4.78 (d, 1H, J
7.7 Hz), 4.93 (d, 1H, J 7.9 Hz), 5.33–5.51 (m, 3H), 5.64–5.90 (m,
4H), 6.03 (t, 1H, J 5.9 Hz), 6.09 (dd, 1H, J 1.7, 17.0 Hz), 7.10–7.69
(m, 21H), 7.70–8.08 (m, 14H); 13C NMR (CDCl3, 50.32 MHz): d
38.9, 60.9, 62.0, 67.4, 69.2, 69.8, 71.3, 71.6. 71.7, 72.5, 73.1, 75.7,
100.9, 101.2, 126.1, 128.1–129.9, 130.3, 133.2, 133.2, 133.3,
133.4, 133.4, 133.4, 133.5, 164.7, 165.1, 165.2, 165.3, 165.3,
½
a 2D5
ꢀ
+29.1 (c 1.5, CHCl3); IR (CHCl3): 3391, 3310, 3064, 2957,
1732, 1669, 1452, 1269, 1177, 1109, 709 cmꢁ1 1H NMR (CDCl3,
;
200.13 MHz): d 3.34–3.68 (m, 2H), 3.77 (ddd, 1H, J 3.2, 7.2,
10.3 Hz), 3.96 (m, 1H), 4.19 (ddd, 1H, J 2.9, 4.9, 7.9 Hz), 4.48 (dd,
1H, J 4.9, 12.2 Hz), 4.71 (dd, 1H, J 2.9, 12.2 Hz), 4.87 (d, 1H, J
8.0 Hz), 5.43 (dd, 1H, J 1.6, 10.2 Hz), 5.54 (dd, 1H, J 8.0, 9.8 Hz),

S. A. Thadke et al. / Carbohydrate Research 346 (2011) 1511–1518
1517
165.3, 165.5, 165.8; HRMS (MALDI-TOF): m/z: calcd for
6.22. Characterization data for compound 17d
[C66H57NO19+Na]+: 1190.3423, found: 1190.3345.
½
a 2D5
ꢀ
+61.3 (c 1.0, CHCl3); IR (CHCl3): 3432, 3374, 3064, 2980,
6.18. 2-(Methacrylamido)ethyl 2,3,6-tri-O-benzoyl-4-O-(2,3,4,6-
1730, 1603, 1501, 1267, 1215, 1096, 769 cmꢁ1 1H NMR (CDCl3,
;
tetra-O-benzoyl-b-
(15b)
D
-galactopyranosyl)-b-
D
-glucopyranoside
200.13 MHz): d 1.01 (d, 3H, J 6.3 Hz), 1.45 (s, 9H), 2.30–2.75 (m,
3H), 2.91 (d, 2H, J 5.2 Hz), 3.74 (s, 3H), 3.87 (m, 1H), 4.06–4.58
(m, 6H), 4.70 (dd, 1H, J 5.1, 9.8 Hz), 4.93 (dd, 1H, J 2.0, 7.8 Hz),
5.40 (d, 1H, J 7.7 Hz), 5.64 (dd, 1H, J 3.4, 10.4 Hz), 5.82 (dd, 1H, J
7.8, 10.4 Hz), 6.02 (d, 1H, J 3.3 Hz), 7.20–7.68 (m, 12H), 7.75–8.14
(m, 8H); 13C NMR (CDCl3, 50.32 MHz): d 16.4, 16.5, 28.2 (6C),
34.9, 35.0, 35.6 (2C), 39.8 (2C), 52.4 (2C), 53.2 (2C), 61.9 (2C),
63.2 (2C), 67.4 (2C), 68.0 (2C), 69.5 (2C), 71.3 (2C), 71.5 (2C),
80.1 (2C), 101.2, 101.3, 128.1–133.0, 133.2 (6C), 133.5 (2C), 155.1
(2C), 165.1 (2C), 165.5 (4C), 166.0 (2C), 171.4 (2C), 174.4, 174.5;
HRMS (MALDI-TOF): m/z: calcd for [C49H53NO16S+Na]+: 966.2983,
found: 966.3002.
½
a 2D5
ꢀ
+46.0 (c 1.2, CHCl3); IR (CHCl3): 3456, 3310, 3086, 2883,
1734, 1603, 1452, 1269, 1095, 756 cmꢁ1 1H NMR (CDCl3,
;
200.13 MHz): d 1.69 (s. 3H), 3.24–3.96 (m, 8H), 4.25 (t, 1H, J
9.5 Hz), 4.48 (dd, 1H, J 4.2, 12.2 Hz), 4.61 (dd, 1H, J 1.6, 12.2 Hz),
4.70 (d, 1H, J 7.8 Hz), 4.88 (d, 1H, J 7.8 Hz), 5.03 (quintet, 1H, J
1.5, 2.3 Hz), 5.34–5.51 (m, 3H), 5.66–5.88 (m, 3H), 6.10 (t, 1H, J
5.3 Hz), 7.10–7.68 (m, 21H), 7.70–8.05 (m, 14H); 13C NMR (CDCl3,
50.32 MHz): d 18.2, 39.1, 61.0, 62.2, 67.4, 69.0, 69.8, 71.3, 71.7,
71.8, 72.6, 73.1, 75.9, 100.9, 101.1, 119.4, 128.2–130.0, 133.2,
133.4, 133.4, 133.4, 133.4, 133.4, 133.5, 139.6, 164.7, 165.2,
165.2, 165.3, 165.4, 165.5, 165.8, 168.2; HRMS (MALDI-TOF): m/
z: calcd for [C67H59NO19+Na]+: 1204.3579, found:1204.3570.
Acknowledgments
S.A.T. and M.K. thank the CSIR-New Delhi for the research fel-
lowship. S.H. thanks the Director, NCL for the LC-MS facility. S.H.
thanks the DST New Delhi for the SwarnaJayanti Fellowship and
S.S.G. thanks the CSIR for research funds (NWP0051-C).
6.19. Characterization data for compound 17a
½
a 2D5
ꢀ
ꢁ56.9 (c 1.0, CHCl3); IR (CHCl3): 3069, 2978, 1724, 1603,
1451, 1215, 758 cmꢁ1 1H NMR (CDCl3, 200.13 MHz): d 1.43 (s,
;
Supplementary data
9H), 2.62–3.08 (m, 6H), 3.74 (s, 3H), 3.75–4.18 (m, 2H), 4.30–4.59
(m, 5H), 4.70 (m, 1H), 5.16 (d, 1H, J 1.6 Hz), 5.47 (d, 1H, J 7.8 Hz),
5.73 (dd, 1H, J 1.8, 3.3 Hz), 5.92 (dd, 1H, J 3.3, 10.1 Hz), 6.14 (t,
1H, J 10.1 Hz), 7.20–7.65 (m, 12H), 7.81–8.15 (m, 8H); 13C NMR
(CDCl3, 50.32 MHz): d 27.5, 28.2 (4C), 34.5, 34.5, 52.5, 53.3, 62.7,
63.7, 66.1, 66.8, 69.0, 69.8, 70.3, 97.7, 128.0–129.9, 133.1, 133.2,
133.4, 133.5, 155.3, 165.3, 165.4, 165.4, 166.1, 171.4, 171.5; HRMS
(MALDI-TOF): m/z: calcd for [C48H51NO16S+Na]+: 952.2826, found:
952.2731.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carres.2011.04.018.
Reference
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6.20. Characterization data for compound 17b
½
a 2D5
ꢀ
ꢁ36.4 (c 1.1, CHCl3); IR (CHCl3): 3420, 3371, 3065, 2978,
1732, 1662, 1452, 1267, 1167, 1097, 756, 712 cmꢁ1 1H NMR
;
(CDCl3, 400.13 MHz): d 1.44 (s, 9H), 2.55 (t, 2H, J 7.1 Hz), 2.83 (t,
2H, J 6.9 Hz), 3.01 (ddd, 2H, J 5.2, 14.5, 18.5 Hz), 3.53 (m, 1H),
3.67–3.77 (m, 5H), 3.94 (dd, 1H, J 4.7, 8.8 Hz), 4.43–4.57 (m, 3H),
4.71 (dd, 1H, J 2.5, 11.8 Hz), 5.13 (s, 1H), 5.54 (d, 1H, J 7.8 Hz),
5.74 (s, 1H), 5.91 (dd, 1H, J 2.9, 10.0 Hz), 6.11 (t, 1H, J 10.0 Hz),
6.53 (br s, 1H), 7.23–7.65 (m, 12H), 7.80–8.11 (m, 8H); 13C NMR
(CDCl3, 100.61 MHz): d 28.2 (3C), 28.4, 34.7, 36.5, 39.1, 52.5,
53.4, 62.8, 66.8, 67.7, 69.0, 70.0, 72.2, 80.2, 97.8, 128.0–129.8,
133.1, 133.3, 133.5, 133.5, 155.2, 165.4, 165.4, 165.6, 166.1,
171.1, 171.5; HRMS (MALDI-TOF): m/z: calcd for [C48H52N2O15SN+-
Na]+: 951.2986, found: 951.2981.
6.21. Characterization data for compound 17c
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½
a 2D5
ꢀ
+42.8 (c 1.3, CHCl3); IR (CHCl3): 3433, 3373, 3070, 2980,
1728, 1603, 1452, 1269, 1176, 1071, 758, 710 cmꢁ1 1H NMR
;
(CDCl3, 200.13 MHz): d 1.44 (s, 9H), 2.22 (t, 2H, J 7.0 Hz), 2.55 (t,
2H, J 7.4 Hz), 2.89 (d, 2H, J 5.2 Hz), 3.74 (s, 3H), 3.69 (m, 3H),
3.80–4.35 (m, 6H), 4.43–4.68 (m, 3H), 4.75 (d, 1H, J 7.8 Hz), 4.88
(d, 1H, J 7.8 Hz), 5.30–5.55 (m, 3H), 5.63–5.90 (m, 3H), 7.09–7.68
(m, 21H), 7.70–8.05 (m, 14H); 13C NMR (CDCl3, 50.32 MHz): d
27.2, 28.2 (3C), 34.0, 34.5, 52.5, 53.1, 61.0, 62.2, 63.1, 67.4, 67.4,
69.8, 71.3, 71.4, 71.7, 72.7, 73.0, 75.9, 80.1, 100.9, 101.0, 128.1–
130.0, 133.2, 133.2, 133.3, 133.4, 133.4, 133.4, 133.5, 155.1,
164.7, 165.0, 165.2, 165.3, 165.3, 165.5, 165.8, 171.3, 171.4; HRMS
(MALDI-TOF): m/z: calcd for [C75H73NO24S+Na]+: 1426.4141,
found: 1426.3896.

1518
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