Synthesis and properties of new bolaform and macrocyclic galactose-based surfactants obtained by olefin metathesis

Article abstract of DOI:10.1016/j.carres.2004.03.003

A series of galactose-based surfactants with various structures likely to display new interesting properties were synthesized. Four monocatenary surfactants were elaborated by microwave-assisted galactosylation of undecanol or 10-undecenol. These compound

Full text of DOI:10.1016/j.carres.2004.03.003

Carbohydrate
RESEARCH
Carbohydrate Research 339 (2004) 1243–1254
Synthesis and properties of new bolaform and macrocyclic
galactose-based surfactants obtained by olefin metathesis
a
Celine Satge, Robert Granet, Bernard Verneuil, Yves Champavier and Pierre Krausz
a
b
a,
*
ꢀ
ꢀ a
aUniversitꢀe de Limoges, Laboratoire de Chimie des Substances Naturelles, 123 Av. Albert Thomas, F-87060 Limoges, France
bUniversitꢀe de Limoges, Service Commun de RMN, Facultꢀe de Pharmacie, 2 rue du Dr Marcland, F-87025 Limoges, France
Received 7 February 2003; received in revised form 1 March 2004; accepted 3 March 2004
Available online 15 April 2004
Abstract—A series of galactose-based surfactants with various structures likely to display new interesting properties were synthe-
sized. Four monocatenary surfactants were elaborated by microwave-assisted galactosylation of undecanol or 10-undecenol. These
compounds were slightly soluble in water. Their tensioactive properties were determined at 45 ꢀC. Olefin metathesis was used to
synthesize the two single-chain bolaforms from undec-10-enyl galactopyranosides; two pseudomacrocyclic bolaforms were prepared
by grafting two carbamates at O-4 and O-40 sugar positions of the single-chain bolaforms. These four surfactants are insoluble in
water and undergo monolayer compression. Cyclization of these bolaforms by olefin metathesis led to macrocyclic surfactant
analogues of archaeobacterial membrane components.
ꢁ 2004 Published by Elsevier Ltd.
Keywords: Surfactant; Bolaform; Metathesis; Microwave
1. Introduction
new interesting properties. This series of nine surfactants
is composed of monocatenary molecules and five bola-
forms of three different kinds: single chain, pseudomac-
rocyclic and macrocyclic (Fig. 1). Monocatenary
surfactants could be used as emulsifiers in food and
cosmetics. Bolaform surfactants, which are composed of
two hydrophilic heads linked by one or several hydro-
phobic chains, are known to promote the formation of
Because of their well-defined chemical composition, their
natural origin and biodegradability, as well as their non-
denaturing properties, sugar-based nonionic surfactants
are interesting additives for use in cosmetic, pharma-
ceutic and food industries.1 We now report on galactose-
based surfactants with varied structures likely to display
single-chain bolaform
carbohydrate
carbohydrate
hydrophobic chain
pseudomacrocyclic bolaform
macrocyclic bolaform
Figure 1. Bolaform surfactant.
* Corresponding author. Tel.: +33-555457475; fax: +33-555457202; e-mail: krausz@unilim.fr
0008-6215/$ - see front matter ꢁ 2004 Published by Elsevier Ltd.
doi:10.1016/j.carres.2004.03.003

1244
C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
ultrathin monolayer membranes.2 As a consequence, the
bolaforms that we synthesized could be used as encap-
sulating agents. Moreover, an interesting property of
many bolaforms is their ability to intercalate into lipidic
membranes; depending on their structure, bolaforms can
act either as membrane disturbing agents or as membrane
stabilizers. Due to the high reactivity and remarkable
functional group tolerance of the new Grubbs’ ruthe-
nium catalysts, olefin metathesis3–5 has recently received
a great deal of interest for the synthesis of complex
molecules. In this paper, we used the homodimerization
reaction6–9 for the building of bolaform surfactants based
on a- and b-galactosides. We also used ring closing
metathesis to form the macrocyclic bolaform.
forms (7a,b), two pseudomacrocyclic bolaforms (15a,b)
and one macrocyclic bolaform (16) (Fig. 2). All of these
products are anomerically pure.
2.1. Syntheses
2.1.1. Synthesis of monocatenary surfactants 3a,b and
8a,b (Scheme 1). We first proceeded to galactosylation of
saturated or x-unsaturated fatty alcohols (compounds
2a,b and 4a,b). Among the numerous methods described
in the literature,14–16 we chose that of Limousin et al.17
using microwave irradiation. This solvent-free reaction
is carried out with a peracetylated carbohydrate 1 and
undecanol or x-undecenol in the presence of zinc chlo-
ride. The best yields (about 90%) were obtained with
2.5 equiv of alcohol and 2.1 equiv of zinc chloride. The
mixtures were irradiated during 2 min at 90 W strength
in the case of undecanol and 60 W in the case of x-
undecenol. Excess alcohol hampered the purification
of the crude galactosides; so the remaining fatty alco-
hols were acetylated with acetic anhydride and N,N-
2. Results and discussion
In the present work, we synthesized a series of galactose-
based surfactants composed of four monocatenary
surfactants (3a,b and 8a,b),10–13 two single-chain bola-
O H
O H
O H
O H
O
O
HO
O
O
(CH2)10 CH3
HO
HO
O H
O H
O
(CH2)10 CH3
3b
3a
O H
O H
O H
O H
O
O
HO
CH2
(CH2)9 CH
O H
O H
CH2
O
(CH2)9 CH
8b
8a
O H
O H
O H
O H
O H
O H
HO
HO
O
O
HO
HO
O
O
(CH2)20
O
HO
HO
O
O H
O H
O H
O
(CH2)20
O
O H
7b
7a
O
O
C
O
C
O
CH2
CH (CH2)8
C
NH
CH2 CH
(CH2)8
C
NH
NH
NH
O
O
O
O
O H
O H
HO
(CH2)8 CH CH2
(CH2)8 CH CH2
HO
O
O
HO
O
HO
O
(CH2)20
O
HO
HO
O
O H
O H
O H
O
(CH2)20
O
O
O H
15b
15a
HN
NH
C
C
O
O H
O H
O
O
HO
O H
O
O
HO
O H
O
O
16
Figure 2. Galactose-based surfactants (a and b refer to a and b compounds, respectively).

C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
1245
O Ac
O H
OAc
O H
O Ac
O Ac
i
ii
O
O
O
ROH
+
AcO
HO
O Ac
AcO
OR
O R
O Ac
O H
O Ac
1
2a,b R = (CH ) -CH
2 10
3
3a,b :α or β undecyl galactoside
8a,b :α or β undecenyl galactoside
4a,b R = (CH ) -CH=CH
2 9
2
Scheme 1. Preparation of monocatenary surfactants. Reagents and conditions: (i) ZnCl2, microwave [2a: 60%, 2b: 29% (a=b ¼ 2:0), 4a: 46%, 4b: 46%
(a/b ¼ 1:0)]; (ii) MeONa, MeOH–CH2Cl2 1:1 (3a: 90%, 3b: 65%, 8a: 74%, 8b: 79%).
dimethyl-4-aminopyridine (DMAP). After separation
on silica gel column, the two anomers were obtained with
anomeric ratios a/b between 1:1 and 2:1 (1H NMR).
Each of the four peracetylated galactosides (2a,b and
4a,b) were deacetylated with sodium methoxide in
methanol–dichloromethane. The yields varied from 65%
to 90%.
2.1.3. Synthesis of pseudomacrocyclic bolaform surfac-
tants 15a,b. In order to synthesize the pseudomacrocyclic
compounds 15a and 15b, we proceeded to a selective
benzoylation of the hydroxyl groups at C-2, C-3 and
C-618 before dimerization. The reactions were carried out
in pyridine at )30 ꢀC and with 4.2 equiv of benzoyl
chloride during 20 min (Scheme 3). a-Galactoside 9a was
obtained with 66% yield while the b-galactoside 9b was
obtained with only 35% yield. The lower reactivity of
OH-418 generally observed in galactosides is thus more
pronounced with the a than with the b anomer. NMR
spectra showed the appearance of 15 aromatic protons
accounting for the three benzoyl groups and the de-
shielding of the carbohydrate moiety. In order to check
that the free hydroxyl is actually at C-4, we analyzed the
differences between perbenzoylated and tribenzoylated
products 9a,b. The most important difference is observed
for H-4. The homodimerization reaction was carried out
as described above and the products 10a and 10b were
obtained in 80% and 77% yield, respectively. In the same
way, catalytic hydrogenation was achieved with rhodium
on alumina and led to products 11a and 11b with yields
of 86% and 88%, respectively.
2.1.2. Synthesis of single-chain bolaformsurfactants 7a,b.
These compounds were obtained by homodimerization
of 4a,b followed by catalytic hydrogenation of the ole-
finic disaccharides (Scheme 2). We proceeded to
homodimerization of a and b peracetylated x-undecen-
yl-D-galactopyranosides 4a,b by olefin metathesis in the
presence of Grubbs’ catalyst I. The reactions were
conducted with catalyst proportions close to 10%
(mol molÀ1). Dimeric compounds were obtained in 83%
1
yield. The H NMR spectra showed the disappearance
of the external double bond signals at 4.95 and 5.81 ppm
and the appearance of two new signals at 5.34 and
5.38 ppm for internal Z and E double bonds, respec-
tively. The E/Z ratio was 1:3 for a-galactosides 5a and of
1:6 for b-galactosides 5b. Catalytic hydrogenation of the
double bond was carried out with rhodium on alumina
as catalyst. In these conditions, the saturated products
6a,b were obtained with quasi-quantitative yields. NMR
spectra showed the disappearance of the ethylenic pro-
tons. Deacetylations of these molecules were carried out
with sodium methoxide in methanol–dichloromethane
to give 7a,b in almost quantitative yields.
The method of Wathier et al.19 was used for the
preparation of x-decenyl isocyanate 13. The corre-
sponding acyl azide was formed by reaction of sodium
azide with x-undecenyl chloride 12 at 10 ꢀC (Scheme 4).
Then, the medium was heated and a Curtius rear-
rangement took place to form compound 13 with 45%
yield.
O Ac
AcO
O Ac
O Ac
AcO
AcO
i
O
O
AcO
O
AcO
AcO
O
O
(CH2)9 CH CH2
O
(CH2)9 CH
CH (CH2)9
O Ac
O Ac
AcO
4a,b
5a,b
PCy3
Ru
O H
O H
HO
O H
Cl
Cl
ii, iii
C
O
HO
HO
O
Ph
O
O
(CH2)20
PCy3
O H
Grubbs' catalyst I
HO
7a,b
Scheme 2. Single-chain bolaforms preparation. Reagents and conditions: (i) Grubbs’ catalyst I (10%), degassed CH2Cl2 (83%); (ii) Rh/Al2O3, H2
(atm pressure), abs EtOH (100%); (iii) MeONa, 1:1 MeOH–CH2Cl2 (95%).

1246
C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
O Bz
HO
O H
HO
i
ii
O
O
BzO
HO
O
(CH2)9 CH CH2
O
(CH2)9 CH CH2
O Bz
O H
8a,b
9a,b
O Bz
O H
O H
O H
O Bz
O H
BzO
BzO
O
O
BzO
O
BzO
O
iii
BzO
BzO
O
O
O
(CH2)9 CH
CH (CH2)9
O
(CH2)20
O Bz
O Bz
BzO
BzO
10a,b
11a,b
O
O
CH CH2
CH CH2
O
CH CH2
O
CH CH2
NH
NH
(CH2)8
(CH2)8
NH (CH2)8
O Bz
NH (CH2)8
O H
O
O
O
O
v
iv
BzO
HO
O
O
BzO
O
HO
O
BzO
HO
O
O
O
(CH2)20
O
(CH2)20
O Bz
O H
14a,b
BzO
HO
15a,b
Scheme 3. Pseudomacrocyclic bolaforms preparation. Reagents and conditions: (i) BzCl (4.2 equiv), anhyd pyridine, ꢀ)30 ꢀC (9a 66%, 9b 35%);
(ii) Grubbs’ catalyst I (9%), degassed CH2Cl2 (ꢀ80%); (iii) Rh/Al2O3, H2, abs EtOH (ꢀ87%); (iv) 13, DABCO, anhyd toluene, 110 ꢀC (ꢀ75%);
(v) MeONa, 10:1 MeOH–CH2Cl2 (ꢀ36%).
O
O
ii
i
CH2 CH
(CH2)8
C
CH2 CH
(CH2)8
C
CH2 CH (CH3)8
N
C
O
Cl
N3
13
12
Scheme 4. Isocyanate formation. Reagents and conditions: (i) NaN3, 10:1 acetone–water, 10 ꢀC; (ii) D (global yield ¼ 45%).
The next step consisted in the coupling reaction of
isocyanate 13 and the selectively protected glycosides
11a and 11b, in order to obtain dicarbamates19 14a,b.
Generally, the reaction of an isocyanate and an alcohol
requires the presence of a strong base. However, the
presence of benzoyl groups restricted the number of
usable bases. For this reason, we decided to use diaza-
bicyclooctane (DABCO) since it does not split ester
bonds. The reaction took place in refluxing toluene at
pH 9 (Scheme 3). Compounds 14a and 14b were
obtained with 79% and 70% yield, respectively. In each
the second generation Grubbs’ catalyst was used
because the first generation catalyst is sensitive to NH
functions. The aim of this methodology was to favour
RCM instead of acyclic diene metathesis (ADMet)
polymerization. Attempts to perform RCM macrocy-
clization of 15a at the water–toluene interphase, in the
presence of dodecyl sulfate, were unsuccessful. Instead,
we decided to cyclize the b anomer (15b) in 8:1 dichloro-
methane–methanol with 1.3 equiv of Grubbs’ catalyst II
during 69 h. NMR and HRMS analyses were consistent
with the structure of the expected macrocycle 16, which
was finally obtained in 33% yield.
1
case, H NMR spectra showed the appearance of a new
terminal double bond.
Removal of benzoyl groups was carried out with
sodium methoxide in 10:1 methanol–dichloromethane
(Scheme 3). The moderate yields (31% and 44% for 15a
and 15b, respectively) can be accounted for by the weak
difference in reactivity between benzoyl and carbamate
groups. The corresponding 1H NMR spectra showed the
expected shielding of the carbohydrate part.
2.2. Tensioactive properties
We first determined the water solubility of each surfac-
tant. All bolaform molecules (single chain 7a and 7b and
pseudomacrocycles 15a and 15b) are insoluble even in
boiling water. However, all galactosides (3a, 3b, 8a and
8b) are partially water soluble. Saturated products are
less soluble than unsaturated ones (Fig. 3) and in each
case, the solubilities of the b galactosides are higher than
their a counterparts. These results are in accordance
with the literature.20 Krafft points were deduced from
2.1.4. Cyclization. In order to obtain macrocyclic bola-
forms, we proceeded to ring closing metathesis (RCM)
of compounds 15a and 15b (Scheme 5). In this reaction,

C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
1247
O
O
CH CH2
O
O
CH CH2
NH
O
NH
(CH2)8
(CH2)8
NH (CH2)8
NH (CH2)8
O H
CH CH
O
O
O H
O
O
i
HO
HO
O
O
HO
O
HO
O
HO
HO
O
O
(CH2)20
O
(CH2)20
O H
O H
HO
HO
15b
16
N
N
Cl
Ru
C
Cl
Ph
PCy3
Grubbs' catalyst II
Scheme 5. Macrocyclization by RCM. Reagents and conditions: (i) Grubbs’ catalyst II (1.3 equiv), degassed 8:1 CH2Cl2–MeOH (33%).
8
6
4
2
0
0
10
20
30
40
50
60
70
80
90
100
Temperature (˚C)
8a
3a
8b
3b
Figure 3. Water solubility of undecyl and undecylenyl galactosides.
the graphs concentration versus temperature. These
values were higher for a anomers as compared to b
anomers, as well as for saturated galactosides compared
to unsaturated ones (Table 1).
Galactoside micellization was studied at 45 ꢀC by
surface tension measurements. According to this meth-
od, the critical micellar concentration (CMC) is equal to
the ordinate of the angular point of the curve ‘surface
tension versus log C’ (Fig. 4). These values that lie
between 0.45 and 3.70 mmol LÀ1, are in accordance with
the literature (CMC ¼ 1.6 mmol LÀ1 for decyl b-gluco-
pyranoside).21 CMC are much lower for saturated
galactosides than for unsaturated ones (Table 2).
The surface excess [C (mol mÀ2)] is calculated from
Gibbs’ equation 1.
10À3
dc
2:3RT d logC
C ¼ À
;
ð1Þ
Table 1. Galactoside Krafft points
Galactoside
Krafft point (ꢀC)
in which c (mN mÀ1) is the surface tension, T , the tem-
perature (K) and C, the concentration (mol LÀ1).
The area per molecule [A (A )] is calculated from
3a
3b
8a
8b
76
46
64
32
2
ꢁ
Eq 2.

1248
C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
60
55
50
45
40
35
30
25
20
galactose configuration has no influence on these values.
The minimal tensions are lower than 30 mN mÀ1. These
results are in accordance with the literature.1;20
Bolaforms and pseudomacrocyclic surfactants (7a, 7b,
15a and 15b), which are insoluble in water, were studied
for their monolayer properties on a home-made Lang-
muir trough (Fig. 5). The minimum area per molecule and
the collapsed pressure were deduced from these data
(Table 3). On the one hand a and b single-chain bolaforms
display the same expanded film behaviour. Their mini-
8a
3a
8b
3b
2
ꢁ
mum area per molecule is close to 150 A . On the other
hand, a and b pseudomacrocyclic bolaforms behave very
2
ꢁ
differently: the b anomer is a condensed film (A ¼ 102 A )
2
ꢁ
and the a anomer is a expanded film (A ¼ 175 A ).
3. Experimental
3.1. General methods
All reagents used were commercially available and with
high purity grade. The microwave reactor was a Syn-
thewaveꢂ 402 (Prolabo). TLC were realized with Silica
Gel 60F254 (direct phase) or RP-18F254 (reversed phase)
(E. Merck). Direct phase chromatography column was
conducted with Silica Gel MCL-CHROM 15–40 lm (E.
Merck). Reversed phase medium pressure chromato-
graphy column was performed on a Jobin Yvon Mini-
prep LC apparatus with Li Chrosorbꢂ RP-18 10 lm
phase (E. Merck).
-5
-4
-3
-2
-1
log C
Figure 4. Surface tension of galactosides at 45 ꢀC.
1020
A ¼
;
ð2Þ
NC
where N is the Avogadro number. Surface excess and
area per molecule are similar for the four galactosides;
Table 2. Surface properties of galactosides
2
CMC (mmol LÀ1
)
Surface excess C (mol mÀ2
)
Minimum surface tension (mN mÀ1
)
ꢁ
Molecular area (A )
8a
8b
3a
3b
3.70
1.66
0.45
0.80
3.90·10À6
3.85·10À6
3.75·10À6
4.03·10À6
43
43
45
42
26.8
29.0
27.4
27.2
35
30
25
20
15
10
5
7a
7b
15a
15b
0
0
100
200
300
400
500
600
²
Area per molecule (Å /molecule)
Figure 5. Compression isotherms of bolaforms and geminis.

C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
1249
and 2b (0.8 g) as yellow oils (89%); 2a: ½aŠ20 +86.0 (c 3.44,
Table 3. Data from compression isotherms for single chain and
pseudomacrocyclic bolaforms
D
CHCl3); Rf 0.33 (7:3 petroleum ether–EtOAc); IR
2
ꢁ
1
Compound
Collapsed pressure
(mN mÀ1
Minimum area A0 (A )
(KBr): m 2920 (CH3), 2849 (CH2) and 1748 (ester); H
)
NMR (CDCl3): d 5.45 (dd, 1H, J3;4 3.2, J4;5 1.0 Hz, H-4),
5.36 (m, 1H, H-1), 5.35 (m, 1H, H-2), 5.10 (m, 1H, H-3),
7a
7b
22
20
31
26
141
158
175
102
0
0
4.22 (te, 1H, J5 ;6 6.8 Hz, H-5), 4.11 (m, 2H, H-6), 3.68
15a
15b
(dt, 1H, J1 a;2 6.6, J1 a;1 b 9.8 Hz, H-10a), 3.42 (dt, 1H,
0
0
0
0
J1 b;2 6.6, J1 a;1 b 9.8 Hz, H-10b), 1.9–2.2 (s, 12H, acetyl),
0
0
0
0
1.59 (m, 2H, H-20), 1.27 (m, 16H, H-30–H-100), 0.88 (t,
Melting points were measured on a Leica VM HB
3H, J10 ;11 6.6 Hz, H-110); lit.12 (CDCl3): 5.49 (dd, J 9.4,
10.4 Hz, H-3), 5.46 (d, J 3.7 Hz, H-1), 5.06 (dd, J 3.6,
10.3 Hz, H-4), 4.86 (dd, J 3.9, 10.4 Hz, H-2), 4.20 (dd, J
2.4, 4.6, 12.2 Hz, H-6b), 4.13 (dd, J 2.4, 4.6, 12.2 Hz, H-
6a), 4.02 (ddd, J 10.3, 4.8, 2.3 Hz, H-5), 3.67 (dt, J 9.6,
10.2, 6.9 Hz, H-1b0), 3.42 (dt, J 9.6, 10.2, 6.9 Hz, H-1a0),
2.02, 2.04, 2.06, 2.10 (4s, OCOCH3), 1.60 (m, H-20), 1.26
(m, H-30–H-100), 0.88 (t, J 6.4 Hz, H-110); ESMS: m=z
0
0
€
system Kofler, NMR spectroscopy was performed with
a Bruker DPX-400 MHz apparatus, IR spectrometry
used a Perkin Elmer FT-IR Spectrometer SPECTRUM
20
D
1000, ½aŠ were measured with a JASCO DIP-370 Dig-
ital Polarimeter, mass spectra using electrospray ioni-
zation were obtained at the Museum National
d’Histoire Naturelle (ESA 8041 CNRS) with a Perkin
Elmer Q TOF SCIEX apparatus, high resolution mass
spectra with electrospray ionization were realized at the
525.19 [M+K]þ. Anal. Calcd for C25H42O10: C, 59.74; H,
20
D
8.42. Found: C, 59.07; H, 8.77. 2b: ½aŠ +2.6 (c 0.80,
ꢀ
‘Centre Regional de Mesures Physiques de l’Ouest,
Universite de Rennes’, with a Varian MAT311 high
CHCl3); Rf 0.24 (7:3 petroleum ether–EtOAc); IR
1
ꢀ
(KBr): m 2920 (CH3), 2849 (CH2) and 1753 (ester); H
resolution spectrometer, elemental analyses were per-
ꢀ
NMR (CDCl3): d 5.39 (dd, 1H, J3;4 3.3, J4;5 0.8 Hz, H-4),
5.20 (dd, 1H, J1;2 8.0, J2;3 10.4 Hz, H-2), 5.02 (dd, 1H, J2;3
10.4, J3;4 3.4 Hz, H-3), 4.45 (d, 1H, J1;2 7.9 Hz, H-1), 4.15
(m, 2H, H-6), 3.88 (m, 2H, H-5 and H-10a), 3.47 (dt, 1H,
formed at the SIARE (Universite Pierre et Marie Curie,
Paris V) or at the Service Central d’Analyse (CNRS,
Vernaison).
All surfactants, except pseudomacrocyclic bolaforms,
were purified on reverse phase medium pressure chro-
matography column before tensioactive properties
determination. Solubilities were measured by using
solutions with defined concentrations. Temperature was
controlled with a Grant Y6 thermostat. Surface tensions
were measured with a Dognon Abribat tensiometer
(Prolabo). The Wilhelmy plate method was used (Pt
plate L ¼ 1:955 cm, e ¼ 0:010 cm). Compression iso-
therms were performed in a home-made rectangular
Teflonꢂ trough (ca. 13.7 · 12.5 cm) with a movable
Teflonꢂ barrier. Each result is the average of three
independent experiments.
J1 b;2 6.8, J1 a;1 b 9.6 Hz, H-10b), 1.9–2.2 (s, 12H, acetyl),
0
0
0
0
1.59 (m, 2H, H-20), 1.26 (m, 16H, H-30–H-100), 0.88 (t,
3H, J10 ;11 6.6 Hz, H-110); lit.12 (CDCl3): d 5.39 (dd, J
0.4, 3.4 Hz, H-4), 5.20 (dd, J 7.8, 10.5 Hz, H-2), 5.02 (dd,
J 3.4, 10.5 Hz, H-3), 4.48 (d, J 7.8 Hz, H-1), 4.20 (dd, J
6.6, 11.3 Hz, H-6b), 4.12 (dd, J 6.6, 11.3 Hz, H-6a), 3.93
(ddd, J 1.0, 6.6, 6.6 Hz, H-5), 3.89 (dt, J 6.7, 10.3,
9.6 Hz, H-1b0), 3.48 (dt, J 6.7, 10.3, 9.6 Hz, H-1a0), 1.98,
2.05, 2.05, 2.15 (4s, OCOCH3), 1.57 (m, H-20), 1.27 (m,
H-30–H-100), 0.88 (t, J 6.7 Hz, H-110); ESMS: m=z 520.34
[M+Na]þ. Anal. Calcd for C25H42O10: C, 59.74; H, 8.42.
Found: C, 59.04; H, 8.70.
0
0
3.2.2. Undecyl a-D-galactopyranoside (3a). Compound
3.2. Syntheses
2a (1.72 g, 3.4 mmol) was dissolved in 1:1 CH2Cl2–
MeOH (50 mL). MeONa (13.5 mL) in MeOH (0.37 g,
6.8 mmol) was added. After 58 min neutralization with
Amberlite IRN 77Hþ resin, filtration and evaporation
3.2.1. Undecyl 2,3,4,6-tetra-O-acetyl-a-D-galactopyrano-
side (2a) and undecyl 2,3,4,6-tetra-O-acetyl-b-
pyranoside (2b). Galactose pentaacetate
D
-galacto-
(2.2 g,
1
yielded 3a as a white solid (1.0 g, 3.1 mmol, 90%); mp
20
D
5.8 mmol) and ZnCl2 (1.7 g, 12 mmol) were crushed to-
gether and undecanol (3 mL, 14 mmol) was added. The
medium was activated by microwave irradiation (2 min,
90 W). It was diluted in EtOAc (100 mL) and suction
filtered. After evaporation of the solvent, DMAP
(0.06 g, 1.7 mmol) and Ac2O (3 mL, 203 mmol) were
added and the medium was activated by microwave
irradiation (1 min, 15 W then 14 min, 6 W), neutralized
(solid NaHCO3) and extracted with CHCl3. The organic
solution was washed with water, dried (MgSO4) and
purified by column chromatography (4:1 petroleum
ether–EtOAc) to give in the order of elution 2a (1.8 g)
55 ꢀC; ½aŠ +114.0 (c 0.88, MeOH); Rf 0.55 (1:1 CHCl3–
EtOH); IR (KBr): m 3440 (alcohol), 2911 (CH3) and
2849 (CH2); 1H NMR (CD3OD): d 4.80 (d, 1H, J1;2
3.2 Hz, H-1), 3.88 (m, 1H, H-3), 3.80 (m, 1H, H-5), 3.71
(m, 5H, H-2, H-4, H-6 and H-10a), 3.43 (dt, 1H, J1 b;2
0
0
6.5, J1 a;1 b 9.6 Hz, H-10b), 1.63 (m, 2H, H-20), 1.29 (m,
16H, H-30–H-100), 0.90 (t, 3H, J10;11 6.6 Hz, H-110);
ESMS: m=z 335.24 [M+H]þ. Anal.þ Calcd for C17H34O6:
C, 61.05; H, 10.25. Found: C, 59.12; H, 10.16.
0
0
3.2.3. Undecyl b-D-galactopyranoside (3b). Deacetylation
of 2b (0.45 g, 0.9 mmol) as above afforded 3b (0.2 g,

1250
C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
20
D
0.6 mmol, 65% yield) as a white solid; mp 72 ꢀC; ½aŠ
After 5 h of reaction the medium was refluxed. Reaction
lasted 21 h. After evaporation, the product was purified
on a silica gel column (4:1 then 1:1 petroleum ether–
EtOAc). A yellow oil was obtained containing a mixture
of Z and E isomers (0.3 g, 0.32 mmol, 83%); Rf 0.44 (1:1
petroleum ether–EtOAc); IR (KBr): m 3018 (internal
olefin), 2920 (CH3), 2850 (CH2), 1748 (ester), 962 (E
olefin) and 755 (Z olefin); 1H NMR (CDCl3): d 5.45 (dd,
2H, J3;4 3.4, J4;5 1.1 Hz, H-4), 5.38 (m, 0.5H, H-100, E),
5.36 (m, 2H, H-2), 5.34 (m, 1.5H, H-100, Z), 5.12 (m, 2H,
H-1), 5.10 (m, 2H, H-3), 4.22 (te, 2H, J5;6 6.2 Hz, H-5),
)10.0 (c 1.02, MeOH); Rf 0.57 (5:5 CHCl3–EtOH); IR
(KBr): m 3354 (alcohol), 2920 (CH3) and 2849 (CH2); 1H
NMR (CD3OD): d 4.20 (d, 1H, J1;2 7.3 Hz, H-1), 3.89
(dt, 1H, J1 a;2 6.9, J1 a;1 b 9.5 Hz, H-10a), 3.82 (d, 1H, J4;5
0
0
0
0
0
0
3.0 Hz, H-5), 3.73 (m, 2H, H-6), 3.53 (dt, 1H, J1 b;2 6.7,
J1 a;1 b 9.4 Hz, H-10b), 3.47 (m, 3H, H-2, H-3 and H-4),
0
0
1.62 (quint, 2H, J1 ;2 ;3 7.0 Hz, H-20), 1.29 (m, 16H, H-30–
0
0
0
H-100), 0.90 (t, 3H, J10 ;11 6.6 Hz, H-110); ESMS: m=z
335.23 [M+H]þ. Anal. Calcd for C17H34O6: C, 61.05; H,
10.25. Found: C, 58.51; H, 10.08.
0
0
0
0
0
0
4.10 (m, 4H, H-6), 3.68 (dt, 2H, J1 a;2 6.5, J1 a;1 b 9.8 Hz,
0
0
0
0
3.2.4. Undec-10-enyl 2,3,4,6-tetra-O-acetyl-a-
pyranoside (4a) and undec-10-enyl 2,3,4,6-tetra-O-acetyl-
b- -galactopyranoside (4b). Galactose pentaacetate 1
(2.2 g, 5.8 mmol) and ZnCl2 (1.6 g, 12 mmol) were cru-
shed together and undecenol (2.9 mL, 14 mmol) was
added. The medium was activated by microwave irra-
diation (2 min, 60 W). It was diluted into EtOAc
(100 mL) and filtrated with suction. After evaporation of
D
-galacto-
H-10a), 3.42 (dt, 2H, J1 b;2 6.6, J1 a;1 b 9.8 Hz, H-10b), 1.9–
2.2 (s, 24H, acetyl), 1.58 (m, 8H, H-20 and H-90), 1.28
(m, 24H, H-30–H-80); ESMS: m=z 973.44 [M+H]þ. Anal.
Calcd for C48H76O20: C, 59.25; H, 7.87. Found: C, 59.09;
H, 8.04.
D
3.2.6. 1,20-Bis(2,3,4,6-tetra-O-acetyl-b-D-galactopyrano-
syloxy)eicos-10-ene (5b). Compound 4b (1.38 g,
2.76 mmol) was dissolved in 10 mL of CH2Cl2 degassed
under Ar. Grubbs’ catalyst (0.09 g, 0.11 mmol) was dis-
solved in the same solvent (15 mL) and added dropwise.
After 23 h, a second portion of catalyst (0.13 g,
0.2 mmol) was added dropwise. Reaction lasted 71 h.
After evaporation, the product was purified on a silica
gel column (4:1 then 1:1 petroleum ether–EtOAc). A
yellow oil was obtained containing a mixture of Z and E
isomers (2.2 g, 2.29 mmol, 83%); Rf 0.38 (1:1 petroleum
ether–EtOAc); IR (KBr): m 3018 (internal olefin), 2920
(CH3), 2850 (CH2), 1748 (ester), 962 (E olefin) and 755
the solvent, DMAP(0.06 g, 1.7 mmol) and Ac O (3 mL,
2
203 mmol) were added and the medium was activated by
microwave irradiation (1 min, 15 W then 14 min, 6 W),
neutralized (solid NaHCO3) and extracted with CHCl3.
The organic solution was washed with water, dried
(MgSO4) and purified by column chromatography (4:1
petroleum ether–EtOAc) to give 4a (1.3 g) and 4b (1.3 g)
20
D
as yellow oils (89%); 4a: ½aŠ +64.3 (c 1.12, CHCl3); Rf
0.31 (7:3 petroleum ether–EtOAc); IR (KBr): m 3018
(terminal olefin), 2920 (CH3), 2849 (CH2) and 1748
1
(ester); H NMR (CDCl3): d 5.81 (m, 1H, H-10), 5.45
1
(de, 1H, J3;4 3.2 Hz, H-4), 5.35 (m, 1H, H-2), 5.11 (m,
1H, H-1), 5.09 (m, 1H, H-3), 4.95 (m, 2H, H-110), 4.22
(te, 1H, J5;6 6.4 Hz, H-5), 4.10 (m, 2H, H-6), 3.68 (dt,
(Z olefin); H NMR (CDCl3): d 5.41 (m, 1.7H, H-100,
E), 5.37 (m, 0.3H, H-100, Z), 5.34 (m, 2H, H-4), 5.20 (dd,
2H, J1;2 8.0, J2;3 10.4 Hz, H-2), 5.01 (dd, 2H, J2;3 10.5, J3;4
3.4 Hz, H-3), 4.45 (d, 2H, J1;2 8.0 Hz, H-1), 4.16 (m, 4H,
H-6), 3.89 (m, 2H, H-5), 3.88 (m, 2H, H-10a), 3.47 (dt,
1H, J1 a;2 6.6, J1 a;1 b 9.8 Hz, H-10a), 3.41 (dt, 1H, J1 b;2
0
0
0
0
0
0
6.6, J1 a;1 b 9.8 Hz, H-10b), 1.9–2.2 (s, 12H, acetyl), 1.58
0
0
(m, 4H, H-20 and H-90), 1.27 (m, 12H, H-30–H-80);
2H, J1 b;2 6.9, J1 a;1 b 9.5 Hz, H-10b), 1.9–2.2 (s, 24H,
acetyl), 1.56 (m, 8H, H-20 and H-90), 1.26 (m, 24H, H-30–
H-80); ESMS: m=z 973.44 [M+H]þ. Anal. Calcd for
C48H76O20: C, 59.25; H, 7.87. Found: C, 58.93; H, 8.08.
0
0
0
0
ESMS: m=z 501.24 [M+H]þ. Anal. Calcd for C25H40O10:
20
D
C, 59.99; H, 8.05. Found: C, 59.53; H, 8.28. 4b: ½aŠ
)3.9 (c 1.03, CHCl3); Rf 0.23 (7:3 petroleum ether–
EtOAc); IR (KBr): m 3018 (terminal olefin), 2920 (CH3),
1
2849 (CH2) and 1753 (ester); H NMR (CDCl3): d 5.81
3.2.7. 1,20-Bis(2,3,4,6-tetra-O-acetyl-a-D-galactopyrano-
(m, 1H, H-10), 5.38 (de, 1H, J3;4 3.3 Hz, H-4), 5.20 (dd,
1H, J1;2 7.9, J2;3 10.3 Hz, H-2), 5.01 (m, 1H, H-3), 4.97
(m, 2H, H-110), 4.45 (d, 1H, J1;2 7.9 Hz, H-1), 4.15 (m,
2H, H-6), 3.88 (m, 2H, H-5 and H-10a), 3.47 (dt, 1H,
syloxy)eicosane (6a). Compound 5a (0.53 g, 0.54 mmol)
was dissolved in abs EtOH (50 mL). Rhodium on alu-
mina was added and the reaction was carried out at
room temperature under H2 atmosphere during 5 h at
0.1 MPa. After filtration and evaporation, a yellow oil
J1 b;2 6.9, J1 a;1 b 9.5 Hz, H-10b), 1.9–2.2 (s, 12H, acetyl),
1.59 (m, 4H, H-20 and H-90), 1.28 (m, 12H, H-30–H-80);
ESMS: m=z 501.24 [M+H]þ. Anal. Calcd for C25H40O10:
C, 59.99; H, 8.05. Found: C, 59.97; H, 8.12.
0
0
0
0
was obtained without further purification (0.53 g,
20
D
0.54 mmol, 100%); ½aŠ +69.1 (c 0.30, CHCl3); Rf 0.44
(1:1 petroleum ether–EtOAc); IR (KBr): m 2920 (CH3),
1
2849 (CH2) and 1748 (ester); H NMR (CDCl3): d 5.45
3.2.5. 1,20-Bis(2,3,4,6-tetra-O-acetyl-a-
D
-galactopyrano-
(de, 2H, J3;4 2.4 Hz, H-4), 5.36 (m, 2H, H-2), 5.12 (m,
2H, H-1), 5.10 (m, 2H, H-3), 4.22 (te, 2H, J5;6 6.4 Hz, H-
syloxy)eicos-10-ene (5a). Compound 4a (0.20 g,
0.39 mmol) was dissolved in CH2Cl2 (2 mL) degassed
under Argon. Grubbs’ catalyst (0.04 g, 0.05 mmol) dis-
solved in the same solvent (10 mL) was added dropwise.
0
0
0
0
5), 4.10 (m, 4H, H-6), 3.67 (dt, 2H, J1 a;2 6.6, J1 a;1 b
9.6 Hz, H-10a), 3.42 (dt, 2H, J1 b;2 6.6, J1 a;1 b 9.6 Hz, H-
0
0
0
0
10b), 1.9–2.2 (s, 24H, acetyl), 1.55 (m, 4H, H-20), 1.26 (m,

C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
1251
32H, H-30–H-100); ESMS: m=z 997.59 [M+K]þ. Anal.
Calcd for C48H78O20: C, 59.12; H, 8.06. Found: C, 59.05;
H, 8.23.
[M+H]þ. Anal.þ Calcd for C17H32O6: C, 61.42; H, 9.70.
Found: C, 59.87; H, 9.92.
3.2.12. Undec-10-enyl b-D-galactopyranoside (8b). De-
acetylation of 4b (0.63 g, 1.3 mmol) as above afforded 8b
3.2.8. 1,20-Bis(2,3,4,6-tetra-O-acetyl-b-
D
-galactopyrano-
20
D
syloxy)eicosane (6b). Compound 5b (0.06 g, 0.07 mmol)
was transformed into 6b using the same procedure as for
6a. A yellow oil (0.06 g, 0.07 mmol, 95%) was obtained;
(0,3 g, 1.0 mmol, 79%) as a white paste; ½aŠ )16.6 (c
0.75, MeOH); Rf 0.55 (1:1 CHCl3–EtOH); IR (KBr): m
3566 (alcohol), 3062 (terminal olefin) and 2850 (CH2);
1H NMR (CD3OD): d 5.80 (m, 1H, H-100), 4.94 (m, 2H,
½aŠ20 )10.6 (c 0.74, CHCl3); Rf 0.38 (1:1 petroleum ether–
D
0
0
EtOAc); IR (KBr): m 2923 (CH3), 2846 (CH2) and 1752
(ester); 1H NMR (CDCl3): d 5.38 (de, 2H, J3;4 3.0 Hz, H-
4), 5.20 (dd, 2H, J1;2 8.0, J2;3 10.3 Hz, H-2), 5.01 (dd, 2H,
J2;3 10.4, J3;4 3.3 Hz, H-3), 4.45 (d, 2H, J1;2 8.0 Hz, H-1),
4.15 (m, 4H, H-6), 3.89 (m, 4H, H-5 and H-10a), 3.47 (dt,
H-110), 4.20 (d, 1H, J1;2 7.6 Hz, H-1), 3.83 (dt, 1H, J1 a;2
7.2, J1 a;1 b 9.4 Hz, H-10a), 3.82 (dd, 1H, J5;6 0.8, J4;5
0
0
0
0
3.0 Hz, H-5), 3.73 (m, 2H, H-6), 3.53 (dt, 1H, J1 b;2 6.4,
J1 a;1 b 9.4 Hz, H-10b), 3.48 (m, 3H, H-2, H-3 and H-4),
0
0
2.04 (quint, 2H, J8 ;9 ;10 7.2 Hz, H-90), 1.62 (quint, 2H,
0
0
0
2H, J1 b;2 6.8, J1 a;1 b 9.4 Hz, H-10b), 1.9–2.2 (s, 24H,
acetyl), 1.56 (m, 4H, H-20), 1.25 (m, 32H, H-30–H-100);
ESMS: m=z 997.51 [M+K]þ. Anal. Calcd for C48H78O20:
C, 59.12; H, 8.06. Found: C, 59.12; H, 8.03.
J1 ;2 ;3 6.8 Hz, H-20), 1.31 (m, 12H, H-30–H-80); lit.10
(CD3OD): d 5.83 (m, 1H, H-100), 4.99 (br d, 1H, J
17.0 Hz, H-110a), 4.93 (br d, 1H, J 17.0 Hz, H-110b), 4.24
(d, 1H, J 7.2 Hz, H-1), 3.90 (m, 3H, H-10a,10b,5), 3.77 (d,
1H,J 6.2 Hz, H-4), 3.63–3.45 (m, 4H, H-6a,6b,2,3), 2.04
(m, 2H, H-90a,b), 1.63 (m, 2H, H-20a,b), 1.43–1.30 (br s,
12H, alkyl protons); ESMS: m=z 333.21 [M+H]þ. Anal.þ
Calcd for C17H32O6: C, 61.42; H, 9.70. Found: C, 59.59;
H, 9.75.
0
0
0
0
0
0
0
3.2.9. 1,20-Bis(a-D-galactopyranosyloxy)eicosane (7a).
Deacetylation of 6a (0.04 g, 0.04 mmol) as above affor-
ded 7a (0.03 g, 0.04 mmol, 98%) as a white solid; mp
20
D
106 ꢀC; ½aŠ +111.6 (c 0.32, MeOH); Rf 0.54 (1:1
CHCl3–EtOH); IR (KBr): m 3376 (alcohol), 2920 (CH3)
and 2849 (CH2); 1H NMR (CD3OD): d 4.80 (d, 2H, J1;2
3.2 Hz, H-1), 3.88 (m, 2H, H-3), 3.80 (m, 2H, H-5), 3.72
3.2.13. Undec-10-enyl 2,3,6-tri-O-benzoyl-a-D-galactopy-
ranoside (9a). Compound 8a (0.16 g, 0.48 mmol) was
dissolved in anhyd pyridine (3.1 mL) at )30 ꢀC under
Ar. BzCl (0.23 mL, 0.28 g, 2.0 mmol) was added drop-
wise (20 min) and the flask was immediately opened.
Pyridine was evaporated (T < 40 ꢀC). The crude product
was dissolved in CHCl3 (30 mL) and washed with 0.1 M
HCl (15 mL), 5% NaHCO3 (15 mL) and water (15 mL).
The organic phase was dried on MgSO4, filtered and
evaporated. After chromatography on a silica gel col-
(m, 10H, H-2, H-4, H-6 and H-10a), 3.43 (dt, 2H, J1 b;2
0
0
6.5, J1 a;1 b 9.6 Hz, H-10b), 1.63 (m, 4H, H-20), 1.29 (m,
32H, H-30–H-100); ESMS: m=z 639.41 [M+H]þ. Anal.
Calcd for C32H62O12: C, 60.16; H, 9.78. Found: C, 58.15;
H, 9.62.
0
0
3.2.10. 1,20-Bis(b-D-galactopyranosyloxy)eicosane (7b).
Deacetylation of 6b (0.32 g, 0.32 mmol) as above affor-
ded 7b (0.19 g, 0.30 mmol, 95%) as a white solid; mp
umn (CHCl3), a yellow paste was obtained (0.20 g,
20
D
20
D
110–117 ꢀC; ½aŠ )10.4 (c 0.85, pyridine); Rf 0.45 (1:1
0.32 mmol, 66%); ½aŠ +93.7 (c 1.41, CHCl3); Rf 0.65
CHCl3–EtOH); IR (KBr): m 3336 (alcohol), 2911 (CH3)
(95:5 CHCl3–EtOH); IR (KBr): m 3487 (alcohol), 3062
(aromatics), 3018 (terminal olefin), 2849 (CH2) and 1717
1
and 2841 (CH2); H NMR (pyridine-d5): d 4.18 (d, 2H,
1
0
0
0
0
J1;2 7.3 Hz, H-1), 3.87 (dt, 2H, J1 a;2 7.0, J1 a;1 b 9.6 Hz, H-
10a), 3.81 (de, 2H, J4;5 2.6 Hz, H-5), 3.70 (m, 4H, H-6),
3.55 (m, 2H, H-10b), 3.48 (m, 6H, H-2, H-3 and H-4),
(ester); H NMR (CDCl3): d 7.2–8.1 (m, 15H, benzoyl),
5.80 (m, 1H, H-100), 5.76 (dd, 1H, J2;3 10.6, J3;4 2.7 Hz,
H-3), 5.66 (dd, 1H, J1;2 3.7, J2;3 10.6 Hz, H-2), 5.30 (d,
1H, J1;2 3.6 Hz, H-1), 4.96 (m, 2H, H-110), 4.67 (dd, 1H,
J5;6a 6.4, J6a;6b 11.4 Hz, H-6a), 4.54 (dd, 1H, J5;6b 6.7,
J6a;6b 11.3 Hz, H-6b), 4.39 (m, 2H, H-4 and H-5), 3.75
1.60 (quint, 4H, J1 ;2 ;3 7.0 Hz, H-20), 1.26 (m, 32H, H-30–
H-100); ESMS: m=z 639.41 [M+H]þ. Anal.þ Calcd for
C32H62O12: C, 60.16; H, 9.78. Found: C, 57.89; H, 9.47.
0
0
0
(dt, 1H, J1 a;2 6.4, J1 a;1 b 9.8 Hz, H-10a), 3.45 (dt, 1H,
0
0
0
0
J1 b;2 6.6, J1 a;1 b 9.8 Hz, H-10b), 2.01 (q, 2H, J8 ;9 ;10
0
0
0
0
0
0
0
3.2.11. Undec-10-enyl a-
Deacetylation of 4a (0.29 g, 0.59 mmol) as above affor-
D
-galactopyranoside (8a).
7.5 Hz, H-90), 1.57 (m, 2H, H-20), 1.18 (m, 12H, H-30–H-
80); ESMS: m=z 667.20 [M+Na]þ. Anal. Calcd for
C38H44O9: C, 70.79; H, 6.88. Found: C, 70.30; H, 7.10.
20
D
ded 8a (0.14 g, 0.44 mmol, 74%) as a white paste; ½aŠ
+101.0 (c 1.10, MeOH); Rf 0.60 (1:1 CHCl3–EtOH); IR
(KBr): m 3336 (alcohol), 3062 (terminal olefin) and 2858
(CH2); H NMR (CD3OD): d 5.80 (m, 1H, H-100), 4.95
3.2.14. Undec-10-enyl 2,3,6-tri-O-benzoyl-b-D-galactopy-
1
(m, 2H, H-110), 4.79 (d, 1H, J1;2 3.6 Hz, H-1), 3.88
(m, 1H, H-3), 3.80 (m, 1H, H-5), 3.72 (m, 5H, H-2, H-4,
ranoside (9b). Compound 8b (1.27 g, 3.8 mmol) was
dissolved in 24.5 mL of anhyd pyridine at )31 ꢀC under
Ar. BzCl (1.86 mL, 2.25 g, 16 mmol) was added dropwise
(20 min) and the flask was immediately opened. Pyridine
was evaporated (T < 40 ꢀC). The crude product was
H-6 and H-10a), 3.43 (dt, 1H, J1 b;2 6.4, J1 a;1 b 9.6 Hz, H-
0
0
0
0
10b), 2.04 (q, 2H, J8 ;9 ;10 7.2 Hz, H-90), 1.62 (m, 2H, H-
0
0
0
20), 1.31 (m, 12H, H-30–H-80); ESMS: m=z 333.22

1252
C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
dissolved in CHCl3 (100 mL) and washed with 0.1 M
HCl (60 mL), 5% NaHCO3 (60 mL) and water (60 mL).
The organic phase was dried on MgSO4, filtered and
evaporated. After chromatography on a silica gel col-
J2;3 10.4, J3;4 3.2 Hz, H-3), 4.72 (d, 2H, J1;2 7.9 Hz, H-1),
4.69 (dd, 2H, J5;6a 6.6, J6a;6b 11.4 Hz, H-6a), 4.61 (dd, 2H,
J5;6b 6.4, J6a;6b 11.4 Hz, H-6b), 4.35 (m, 2H, H-4), 4.07
0
0
0
0
(te, 2H, J4;5;6 6.5 Hz, H-5), 3.91 (dt, 2H, J1 a;2 6.2, J1 a;1 b
9.7 Hz, H-10a), 3.52 (dt, 2H, J1 b;2 6.7, J1 a;1 b 9.6 Hz, H-
10b), 1.93 (m, 4H, H-90), 1.51 (m, 4H, H-20), 1.23 (m,
24H, H-30–H-80); ESMS: 1283.43 [M+Na]þ. Anal. Calcd
for C74H84O18: C, 70.46; H, 6.71. Found: C, 69.27; H,
7.06.
0
0
0
0
umn (9:1 CHCl3–petroleum ether) a yellow paste was
20
D
obtained (0.86 g, 1.33 mmol, 35%); ½aŠ +33.4 (c 0.99,
CH2Cl2); Rf 0.47 (49:1 CHCl3–EtOH); IR (KBr): m 3487
(alcohol), 3062 (aromatics), 3018 (terminal olefin), 2849
(CH2) and 1717 (ester); 1H NMR (CDCl3): d 7.3–8.1 (m,
15H, benzoyl), 5.80 (m, 1H, H-100), 5.75 (dd, 1H, J1;2
8.0, J2;3 10.2 Hz, H-2), 5.35 (dd, 1H, J2;3 10.3, J3;4 3.2 Hz,
H-3), 4.96 (m, 2H, H-110), 4.71 (d, 1H, J1;2 7.9 Hz, H-1),
4.69 (dd, 1H, J5;6a 6.6, J6a;6b 11.4 Hz, H-6a), 4.61 (dd, 1H,
J5;6b 6.4, J6a;6b 11.4 Hz, H-6b), 4.35 (dd, 1H, J3;4 3.2, J4;5
5.2 Hz, H-4), 4.07 (te, 1H, J4;5;6 6.5 Hz, H-5), 3.91 (dt,
3.2.17. 1,20-Bis(2,3,6-tri-O-benzoyl-a-D-galactopyrano-
syloxy)eicosane (11a). Compound 10a (0.15 g,
0.12 mmol) was transformed into 11a using the same
procedure as for 6a. A yellow oil (0.13 g, 0.10 mmol,
20
D
86%) was obtained; ½aŠ +122.7 (c 0.42, CHCl3); Rf 0.21
1H, J1 a;2 6.2, J1 a;1 b 9.7 Hz, H-10a), 3.52 (dt, 1H, J1 b;2
(49:1 CHCl3–EtOH); IR (KBr): m 3442 (alcohol), 3070
(aromatics), 2849 (CH2) and 1717 (ester); 1H NMR
(CDCl3): d 7.3–8.1 (m, 30H, benzoyl), 5.76 (dd, 2H, J2;3
10.6, J3;4 3.0 Hz, H-3), 5.67 (dd, 2H, J1;2 3.6, J2;3 10.6 Hz,
H-2), 5.30 (d, 2H, J1;2 3.6, H-1), 4.67 (dd, 2H, J5;6a 5.8,
J6a;6b 11.5 Hz, H-6a), 4.54 (dd, 2H, J5;6b 6.8, J6a;6b
11.4 Hz, H-6b), 4.39 (m, 4H, H-4 and H-5), 3.76 (dt, 2H,
0
0
0
0
0
0
6.6, J1 a;1 b 9.6 Hz, H-10b), 2.01 (q, 2H, J8 ;9 ;10 6.9 Hz, H-
90), 1.51 (m, 2H, H-20), 1.17 (m, 12H, H-30–H-80); ESMS:
m=z 645.30. Anal. Calcd for C38H44O9: C, 70.79; H, 6.88.
Found: C, 70.62; H, 7.01.
0
0
0
0
0
3.2.15. 1,20-Bis(2,3,6-tri-O-benzoyl-a-D-galactopyrano-
J1 a;2 6.4, J1 a;1 b 9.8 Hz, H-10a), 3.45 (dt, 2H, J1 b;2 6.6,
0
0
0
0
0
0
syloxy)eicos-10-ene (10a). Compound 9a (0.25 g,
0.39 mmol) was dissolved in 1.8 mL CH2Cl2 degassed
under Ar. Grubbs’ catalyst (0.03 g, 0.04 mmol) was dis-
solved in the same solvent (10 mL) and added dropwise.
Reaction lasted 21 h. After evaporation the product was
purified on a silica gel column (49:1 CHCl3–EtOH). A
yellow paste was obtained (0.39 g, 0.31 mmol,
yield ¼ 80%); Rf 0.21 (49:1 CHCl3–EtOH); IR (KBr): m
3487 (alcohol), 3062 (aromatics), 3018 (internal olefin),
2849 (CH2), 1721 (ester), 971 (E olefin) and 711 (Z
J1 a;1 b 9.8 Hz, H-10b), 1.56 (m, 4H, H-20), 1.23 (m, 32H,
H-30–H-100); ESMS: m=z 1285.58 [M+Na]þ. Anal. Calcd
for C74H86O18: C, 70.35; H, 6.86. Found: C, 69.91; H,
6.97.
0
0
3.2.18. 1,20-Bis(2,3,6-tri-O-benzoyl-b-D-galactopyrano-
syloxy)eicosane (11b). Compound 10b (0.16 g,
0.13 mmol) was transformed into 11b using the same
procedure as for 6a. A yellow oil (0.14 g, 0.11 mmol,
20
D
1
olefin); H NMR (CDCl3): d 7.3–8.1 (m, 30H, benzoyl),
88%) was obtained; ½aŠ )121.1 (c 1.43, CHCl3); Rf 0.33
5.75 (dd, 2H, J2;3 10.6, J3;4 3.0 Hz, H-3), 5.67 (dd, 2H, J1;2
3.6, J2;3 10.6 Hz, H-2), 5.37 (m, 2H, H-100), 5.30 (d, 2H,
J1;2 3.6, H-1), 4.67 (dd, 2H, J5;6a 5.8, J6a;6b 11.4 Hz, H-
6a), 4.54 (dd, 2H, J5;6b 6.7, J6a;6b 11.3, H-6b), 4.39 (m,
(49:1 CHCl3–EtOH); IR (KBr): m 3452 (alcohol), 3068
(aromatics), 2836 (CH2) and 1718 (ester); 1H NMR
(CDCl3): d 7.3–8.1 (m, 30H, benzoyl), 5.75 (dd, 2H, J1;2
7.9, J2;3 10.3 Hz, H-2), 5.35 (dd, 2H, J2;3 10.3, J3;4 3.2 Hz,
H-3), 4.71 (d, 2H, J1;2 7.9 Hz, H-1), 4.69 (dd, 2H, J5;6a
6.6, J6a;6b 11.5 Hz, H-6a), 4.61 (dd, 2H, J5;6b 6.4, J6a;6b
11.4 Hz, H-6b), 4.35 (dd, 2H, J3;4 3.2, J4;5 5.3 Hz, H-4),
0
0
0
0
4H, H-4 and H-5), 3.75 (dt, 2H, J1 a;2 6.4, J1 a;1 b 9.8 Hz,
H-10a), 3.44 (dt, 2H, J1 b;2 6.5, J1 a;1 b 9.7 Hz, H-10b), 1.93
(m, 4H, H-90), 1.55 (m, 4H, H-20), 1.18 (m, 24H, H-30–H-
80); ESMS: m=z 1283.43 [M+Na]þ. Anal. Calcd for
C74H84O18: C, 70.46; H, 6.71. Found: C, 70.15; H, 6.82.
0
0
0
0
0
0
4.07 (te, 2H, J4;5;6 6.5 Hz, H-5), 3.91 (dt, 2H, J1 a;2 6.2,
J1 a;1 b 9.7 Hz, H-10a), 3.52 (dt, 2H, J1 b;2 6.7, J1 a;1 b
9.6 Hz, H-10b), 1.51 (m, 4H, H-20), 1.20 (m, 32H, H-30–
H-100); ESMS: m=z 1285.45 [M+Na]þ. Anal. Calcd for
C74H86O18: C, 70.35; H, 6.86. Found: C, 68.83; H, 6.63.
0
0
0
0
0
0
3.2.16. 1,20-Bis(2,3,6-tri-O-benzoyl-b-D-galactopyrano-
syloxy)eicos-10-ene (10b). Compound 9b (0.25 g,
0.39 mmol) was dissolved in 1.8 mL of CH2Cl2 degassed
under Ar. Grubbs’ catalyst (0.03 g, 0.04 mmol) was dis-
solved in the same solvent (10 mL) and added dropwise.
Reaction lasted 21 h. After evaporation, the product was
purified on a silica gel column (49:1 CHCl3–EtOH). A
yellow paste was obtained (0.38 g, 0.30 mmol, 77%); Rf
0.33 (49:1 CHCl3–EtOH); IR (KBr): m 3487 (alcohol),
3062 (aromatics), 3031 (internal olefin), 2849 (CH2),
3.2.19. Dec-9-enylisocyanate (13). 10-Undecenyl chloride
(12; 2.5 mL, 2.36 g, 18 mmol) was dissolved in 100 mL of
acetone. Sodium azide (3.1 g, 49 mmol) was dissolved in
10 mL cold water (T < 10 ꢀC) and 12 was added drop-
wise. The reaction lasted 2 h at 10–15 ꢀC. Then, 300 mL
cold petroleum ether were added and the medium was
stirred until NaCl was dissolved. The organic phase was
dried on MgSO4 and distilled under diminished pres-
sure. A colourless liquid was obtained (1.47 g, 8.1 mmol,
45%); d 0.82; IR (KBr): m 3080 (terminal olefin), 2849
1
1722 (ester), 988 (E olefin) and 706 (Z olefin); H NMR
(CDCl3): d 7.3–8.1 (m, 30H, benzoyl), 5.75 (dd, 2H, J1;2
7.9, J2;3 10.3 Hz, H-2), 5.36 (m, 2H, H-100), 5.35 (dd, 2H,

C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
1253
1
1
(CH2) and 2265 (isocyanate); H NMR (CDCl3): d 5.81
3037 (terminal olefin), 2849 (CH2) and 1726 (ester); H
NMR (CDCl3): d 7.3–8.2 (m, 30H, benzoyl), 5.81 (m,
2H, H-900), 5.69 (dd, 2H, J1;2 8.0, J2;3 10.4 Hz, H-2), 5.63
(de, 2H, J3;4 3.0, H-4), 5.45 (dd, 2H, J2;3 10.4, J3;4 3.3 Hz,
H-3), 4.96 (m, 4H, H-1000), 4.72 (d, 2H, J1;2 7.9 Hz, H-1),
4.62 (m, 2H, H-6a), 4.32 (m, 2H, H-6b), 4.20 (m, 2H,
H-5), 3.91 (m, 2H, H-10a), 3.51 (m, 2H, H-10b), 3.02 (m,
4H, H-100), 2.02 (m, 4H, H-800), 1.60 (m, 4H, H-20), 1.36
(m, 4H, H-200), 1.23 (m, 52H, H-30–H-100 and H-300–H-
700); 13C NMR: d 165–167 (quaternary carbons from
benzoyls), 155.1 (quaternary carbon from carbamate),
139.2 (C-900), 128–131 (aromatic carbons from benzoyls),
114.2 (C-1000), 101.5 (C-1), 72.0 (C-3), 71.3 (C-5), 70.5
(C-10), 69.9 (C-2), 68.0 (C-4), 62.1 (C-6), 41.2 (C-100),
33.8 (C-800), 25–30 (C-20–C-100 and C-200–C-700); ESMS:
m=z 1647.87 [M+Na]þ. Anal. Calcd for C96H124N2O20:
C, 70.91; H, 7.69; N, 1.72. Found: C, 71.12; H, 7.66; N,
1.74.
(m, 1H, H-9), 4.97 (m, 2H, H-10), 3.29 (t, 2H, J1;2
6.7 Hz, H-1), 2.04 (q, 2H, J7;8;9 7.4 Hz, H-8), 1.61 (quint,
2H, J1;2;3 7.0 Hz, H-2), 1.37 (m, 2H, H-7), 1.30 (m, 8H,
H-3-H-6); 13C NMR: d 139.3 (C-9), 122.0 (quaternary
carbon), 114.4 (C-10), 43.6 (C-8), 33.8 (C-1), 26–30 (C-
2–C-7); CIMS: m=z 182 [M+H]þ.
3.2.20. 1,20-Bis[2,3,6-tri-O-benzoyl-4-O-(N-dec-9-enyl)-
carbamoyl-a-
D
-galactopyranosyloxy]eicosane
(14a).
Compound 11a (0.04 g, 0.03 mmol) was dissolved in
anhyd toluene (2 mL) 13 (0.03 g, 0.14 mmol) and DAB-
CO (0.01 g, 0.08 mmol dissolved in 0.05 mL anhyd tol-
uene) were added. Reaction lasted 4 h at 110 ꢀC. After
evaporation, the crude product was dissolved in 20 mL
CHCl3 and washed with HCl 0.1 M (3 · 10 mL) and
saturated NaHCO3 (3 · 10 mL). The organic phase was
dried on MgSO4, filtered and evaporated. After purifi-
cation on silica preparative TLC (99:1 chloroform–eth-
anol) a white paste was obtained (0.04 g, 0.11 mmol,
79%); ½aŠ +128.8 (c 0.51, CH2Cl2); Rf 0.56 (49:1
3.2.22. 1,20-Bis[4-O-(N-dec-9-enyl)carbamoyl-a-D-galac-
20
D
topyranosyloxy]eicosane (15a). Compound 14a (0.16 g,
0.10 mmol) was dissolved in MeONa (10 mL) in MeOH
(0.27 g, 5 mmol). CH2Cl2 (2 mL) was added. Reaction
lasted 16 h, TLC indicated the reaction was complete.
After neutralization with Amberlite IRN 77Hþ resin,
filtration, evaporation and purification on silica gel
CHCl3–EtOH); IR (KBr): m 3452 and 1726 (carbamate),
3062 (aromatics), 3031 (terminal olefin), 2849 (CH2) and
1726 (ester); 1H NMR (CDCl3): d 7.3–8.2 (m, 30H,
benzoyl), 5.86 (dd, 2H, J2;3 10.7, J3;4 3.3 Hz, H-3), 5.78
(m, 2H, H-900), 5.67 (m, 2H, H-4), 5.56 (dd, 2H, J1;2 3.6,
J2;3 10.7 Hz, H-2), 5.28 (d, 2H, J1;2 3.5 Hz, H-1), 4.96 (m,
4H, H-1000), 4.56 (m, 2H, H-6a), 4.53 (m, 2H, H-5), 4.37
(m, 2H, H-6b), 3.73 (m, 2H, H-10a), 3.43 (m, 2H, H-10b),
3.07 (m, 4H, H-100), 2.02 (m, 4H, H-800), 1.56 (m, 4H, H-
20), 1.34 (m, 4H, H-200), 1.22 (m, 52H, H-30–H-100 and H-
300–H-700); 13C NMR: d 165–166 (quaternary carbons
from benzoyls), 155.2 (quaternary carbon from carba-
mate), 139.2 (C-900), 128–134 (aromatic carbons from
benzoyls), 114.2 (C-1000), 96.4 (C-11), 69.3 (C-2), 69.1
(C-4), 68.7 (C-10), 68.4 (C-3), 67.0 (C-5), 62.9 (C-6), 41.2
(C-100), 33.8 (C-800), 26–30 (C-20–C-100 and C-200–C-700);
ESMS: m=z 1647.87 [M+Na]þ. Anal. Calcd for
C96H124O20N2: C, 70.91; H, 7.69; N, 1.72. Found: C,
70.72; H, 7.90; N, 1.75.
column (9:1 then 85:15 CHCl3–EtOH) a white solid was
20
D
obtained (0.03 g, 0.03 mmol, 31%); mp 80 ꢀC; ½aŠ +43.4
(c 0.31, 4:1 CHCl3–MeOH); Rf 0.39 (4:1 CHCl3–EtOH);
IR (KBr): m 3434, 1726 and 1638 (carbamate), 3434
(alcohol), 3071 (aromatics), 3031 (terminal olefin), 2849
1
(CH2) and 1726 (ester); H NMR (CDCl3): d 5.81 (m,
2H, H-900), 4.95 (m, 4H, H-1000), 4.89 (d, 2H, J1;2 2.6 Hz,
H-1), 4.33 (dd, 2H, J5;6a 5.4, J6a;6b 11.3 Hz, H-6a), 4.15
(dd, 2H, J5;6b 7.2, J6a;6b 11.4 Hz, H-6b), 3.80–3.94 (m,
0
0
6H, H-2, H-3, H-4 and H-5), 3.67 (dt, 2H, J1 a;2 7.0,
J1 a;1 b 9.3 Hz, H-10a), 3.45 (dt, 2H, J1 b;2 6.5, J1 a;1 b
0
0
0
0
0
0
9.6 Hz, H-10b), 3.14 (t, 4H, J1 7.0 Hz, H-100), 2.03 (q,
4H, J7
00 ;200
6.8 Hz, H-800), 1.60 (m, 4H, H-20), 1.48 (m,
00 ;800 ;900
4H, H-200), 1.27 (m, 52H, H-30–H-100 and H-300–H-700);
13C NMR: d 156.6 (quaternary carbon), 139.1 (C-900),
114.1 (C-1000), 98.5 (C-1), 68.3 69.0 (·2), 70.3 (C-2 C-3
C-4 C-5), 68.4 (C-10), 63.5 (C-6), 40.9 (C-100), 33.7 (C-800),
22–31 (C-20–C-100 and C-200–C-700); ESMS: m=z 1002.75
[M+H]þ. Anal. Calcd for C54H100N2O14: C, 64.77; H,
10.07; N, 3.00. Found: C, 63.41; H, 10.01; N, 2.72.
3.2.21. 1,20-Bis[2,3,6-tri-O-benzoyl-4-O-(N-dec-9-enyl)-
carbamoyl-b-
D
-galactopyranosyloxy]eicosane
(14b).
Compound 11b (0.14 g, 0.11 mmol) was dissolved in
anhyd toluene (7 mL). Compound 13 (0.10 g, 0.56 mmol)
and DABCO (0.006 g, 0.05 mmol in 0.03 mL anhyd
toluene) were added. Reaction lasted 23 h at 110 ꢀC,
TLC indicated the reaction was complete. After evapo-
ration, the crude product was dissolved in 30 mL CHCl3
and washed with HCl 0.1 M (3 · 15 mL) and saturated
NaHCO3 (3 · 15 mL). The organic phase was dried on
MgSO4, filtered and evaporated. After purification on
3.2.23. 1,20-Bis[4-O-(N-dec-9-enyl)carbamoyl-b-D-galac-
to- pyranosyloxy]eicosane (15b). Compound 14b
(0.11 g, 0.07 mmol) was dissolved in 2 mL of MeONa in
MeOH (0.005 g, 0.1 mmol). CH2Cl2 (1 mL) was added.
Reaction lasted 16 h, TLC indicated the reaction was
complete. After neutralization with Amberlite IRN
77Hþ resin, filtration, evaporation and purification on
silica gel column (9:1 then 4:1 CHCl3–EtOH) a white
solid was obtained (0.03 g, 0.03 mmol, 44%); mp 90 ꢀC;
silica preparative TLC [eluent CH2Cl2 (2·)] a white
20
paste was obtained (0.13 g, 0.8 mmol, 70%); ½aŠ +42.7
D
(c 1.22, CHCl3); Rf 0.35 (99:1 CHCl3–EtOH); IR (KBr):
m 3434, 1726 and 1638 (carbamate), 3071 (aromatics),

1254
20
C. Satgꢀe et al. / Carbohydrate Research 339 (2004) 1243–1254
½aŠ +23.8 (c 0.29, 1:1 CHCl3–MeOH); Rf 0.37 (4:1
Acknowledgements
D
CHCl3–EtOH); IR (KBr): m 3434, 1726 and 1642 (car-
bamate), 3434 (alcohol), 3080 (terminal olefin), 2849
ꢀ
We thank the ‘Conseil Regional du Limousin’ for
1
(CH2) and 1726 (ester); H NMR (CDCl3): d 5.81 (m,
financial support. We are also grateful to Dr. Jean-Paul
Brouard for mass spectra, Dr. Michel Guilloton for help
in manuscript preparation and to Dr. Rachida Ben-
haddou-Zerrouki for helpful discussion.
2H, H-900), 4.95 (m, 4H, H-1000), 4.28 (m, 4H, H-6), 4.21
0
0
0
0
(d, 2H, J1;2 7.1 Hz, H-1), 3.88 (dt, 2H, J1 a;2 7.0, J1 a;1 b
9.4 Hz, H-10a), 3.84 (de, 2H, J3;4 2.4 Hz, H-4), 3.65 (m,
2H, H-5), 3.53 (m, 6H, H-2, H-3 and H-10b), 3.13 (t, 4H,
J1
7.1 Hz, H-100), 2.04 (q, 4H, J7
6.8 Hz, H-800),
00 ;200
00 ;800 ;900
1.62 (quint, 4H, J1 ;2 ;3 6.9 Hz, H-20), 1.49 (quint, 4H,
J1
6.0 Hz, H-200), 1.26 (m, 52H, H-30–H-100 and H-
0
0
0
00 ;200 ;300
References
300–H-700); 13C NMR: d 156.9 (quaternary carbon), 139.3
(C-900), 114.2 (C-1000), 103.3 (C-1), 71.5 and 73.4 (C-2
and C-3), 72.7 (C-5), 70.3 (C-10), 68.4 (C-4), 63.0 (C-6),
41.1 (C-100), 33.9 (C-800), 28–30 (C-20–C-100 and C-200–C-
700); ESHRMS: calcd for C54H100N2O14Naþ: 1023.7072.
Found: 1023.7063. Anal. Calcd for C54H100N2O14: C,
64.77; H, 10.07; N, 3.00. Found: C, 63.73; H, 9.79; N,
2.77.
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15. Lubineau, A.; Fischer, J. C. Synth. Commun. 1991, 815–
818.
16. Nicolaou, K. C.; Hummel, C. W.; Iwabuchi, Y. J. Am.
Chem. Soc. 1992, 114, 3126–3128.
1
(4:1 CHCl3–EtOH); H NMR (CDCl3): d 5.32 (m, 2H,
H-900), 4.28 (m, 4H, H-6), 4.21 (d, 2H, J1;2 7.1 Hz, H-1),
3.88 (dt, 2H, J1 a;2 7.0, J1 a;1 b 9.4 Hz, H-10a), 3.84 (de,
2H, J3;4 2.4 Hz, H-4), 3.65 (m, 2H, H-5), 3.53 (m, 6H, H-
0
0
0
0
2, H-3 and H-10b), 3.13 (t, 4H, J1
7.1 Hz, H-100), 2.04
00 ;200
ꢀ
17. Limousin, C.; Cleophax, J.; Petit, A.; Loupy, A.; Lukacs,
6.8 Hz, H-800), 1.62 (quint, 4H, J1 ;2 ;3
00 ;800 ;900
(q, 4H, J7
0
0
0
G. J. Carbohydr. Chem. 1997, 16, 327–342.
18. Williams, J. M.; Richardson, A. C. Tetrahedron 1967, 23,
1369–1378.
19. Wathier, M.; Polidori, A.; Ruiz, K.; Fabiano, A. S.; Pucci,
B. New J. Chem. 2001, 25, 1588–1599.
20. Van Buuren, A. R.; Berendsen, H. J. C. Langmuir 1994,
10, 1703–1713.
21. Boyd, B. J.; Drummond, C. J.; Krodkiewska, I.; Grieser,
F. Langmuir 2000, 16, 7359–7367.
6.9 Hz, H-20), 1.49 (quint, 4H, J1
6.0 Hz, H-200), 1.26
00 ;200 ;300
(m, 52H, H-30–H-100 and H-300–H-700); ESHRMS: calcd
for C52H96N2O14Naþ: 995.5759. Found: 995.5748.
Note: þMelting under diminished pressure did not
improve the elemental analysis data for 3a, 3b, 7a, 7b,
8a, 8b, 15a, 15b, which then exceed the admitted devi-
ation range from the theory.