Synthesis and mesomorphic properties of glycosyl dialkyl- and diacyl-glycerols bearing saturated, unsaturated and methyl branched fatty acid and fatty alcohol chains: Part I. Synthesis

Article abstract of DOI:10.1016/j.chemphyslip.2005.01.004

Glycosyl dialkyl- and diacyl-glycerols bearing saturated, unsaturated or chiral methyl branched chains in the tail and disaccharide and trisaccharide carbohydrate headgroups were synthesised. Standard procedures were used for the preparation of the educts and the glyco lipids: trichloracetimidate procedure for the preparation of long-chained compounds, glycosylation using the β-peracetate and boron trifluoride etherate was successful for the preparation of lipids with a medium-alkyl chain length. Preparation of the ester was afforded in a multi-step synthesis according to published procedures. Thus, several lipids were synthesised in a few synthetic steps in good yields. The introduction of unsaturated or methyl branched chains lead to liquid crystallinity at ambient temperature, because these compounds will be used as model compounds for biological systems. The biophysical properties of these compounds will be reported in a following paper.

Full text of DOI:10.1016/j.chemphyslip.2005.01.004

Chemistry and Physics of Lipids 135 (2005) 1–14
Synthesis and mesomorphic properties of glycosyl dialkyl- and
diacyl-glycerols bearing saturated, unsaturated and methyl
branched fatty acid and fatty alcohol chains
Part I. Synthesis
a
a
b
c
a, ∗
¨
Gotz Milkereit , Sven Gerber , Klaus Brandenburg , Michael Morr , Volkmar Vill
a
Institute of Organic Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
b
Research Center Borstel, Leibniz-Zentrum fu¨r Medizin und Biowissenschaften, Parkallee 10, 23845 Borstel, Germany
c
Gesellschaft fu¨r Biotechnologische Forschung mbH, Mascheroder Weg 1, 38124 Braunschweig, Germany
Received 22 July 2004; received in revised form 13 January 2005; accepted 14 January 2005
Available online 25 February 2005
Abstract
Glycosyl dialkyl- and diacyl-glycerols bearing saturated, unsaturated or chiral methyl branched chains in the tail and disac-
charide and trisaccharide carbohydrate headgroups were synthesised. Standard procedures were used for the preparation of the
educts and the glyco lipids: trichloracetimidate procedure for the preparation of long-chained compounds, glycosylation using
the ␤-peracetate and boron trifluoride etherate was successful for the preparation of lipids with a medium-alkyl chain length.
Preparation of the ester was afforded in a multi-step synthesis according to published procedures. Thus, several lipids were
synthesised in a few synthetic steps in good yields. The introduction of unsaturated or methyl branched chains lead to liquid
crystallinity at ambient temperature, because these compounds will be used as model compounds for biological systems. The
biophysical properties of these compounds will be reported in a following paper.
© 2005 Elsevier Ireland Ltd. All rights reserved.
Keywords: Glyco glycero lipids; Synthesis; Branched fatty acids; Trichloracetimidate procedure
1. Introduction
as important constituents in cell membranes. In prin-
ciple, these lipids consist of a carbohydrate head-
group as polar head while the unpolar tail is build up
by glycerol esters or ethers of alkyl or acyl chains
(Ishizuka and Yamakawa, 1985). Lipids with small
headgroups (1–3 carbohydrate units in the head) can
be found as major components of the cell mem-
brane, whereas the more complex lipids are in-
Glyco glycero lipids are known to be an impor-
tant class of glycolipids. These lipids can be found
DOI of original article:10.1016/j.chemphyslip.2005.01.007.
Corresponding author. Tel.: +49 40 42838 4269;
∗
fax: +49 40 42838 7815.
E-mail address: vill@liqcryst.chemie.uni-hamburg.de (V. Vill).
0009-3084/$ – see front matter © 2005 Elsevier Ireland Ltd. All rights reserved.
doi:10.1016/j.chemphyslip.2005.01.004

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G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
volved in cell surface recognition processes (Curatolo,
1987).
The mesomorphic properties of the synthesised
compounds are presented in a following paper
(Milkereit et al., 2004, in press).
In a preceding paper, we reported about the synthe-
sis of glycosyl diacyl-glycerols with monosaccharide
and disaccharide headgroups (Minden et al., 2002a),
with unsaturated and chiral methyl branched fatty
acid chains. These molecules showed liquid crystalline
phases already at ambient temperature so biophysi-
cal properties could be investigated in the temperature
range of biological systems (Minden et al., 2002b).
The great disadvantage of these compounds is the
synthesis. The synthesis of a single diacyl-glycerol
with unsaturated fatty acid chains requires at least nine
synthetic steps, and the overall yield will be in the range
of 3–26%.
2. Results and discussion
First three different types of 1,3-substituted glyc-
erols were synthesised using standard procedures (see
for example, Bebernitz et al., 2001).
Synthesis of 1,3-di-O-tetradecyl-sn-glycerol and
1,3-di-O-(oleyl)-sn-glycerol is already described in the
literature (see for example, Altenburger et al., 1992;
Bear and Stanacev, 1965; Paltauf and Johnston, 1971).
The chiral methyl branched fatty acid (2R,4R,
6R,8R)-2,4,6,8-tetramethyldecanoic acid and the
corresponding alcohol (2R,4R,6R,8R)-2,4,6,8-tetra-
methyldecanol were prepared from natural source
as described by Morr et al. (1992, 1997). Using
extracts from the preen glands of the domestic goose
(Anser a.f. domesticus), the acid was prepared in a
multi-step synthesis by transesterification, Spaltrohr
distillation and saponification of the fatty acid methyl
ester. The alcohol was prepared by reduction of the
fatty acid methyl ester instead of the saponification
step. The fatty acid and the alcohol were obtained
with a diastereomeric excess of more than 99%.
The alcohol was used for the synthesis of the new
glycerol 3. The fatty acid was used for the synthesis
of the diacyl-glycerol instead, as described below.
The synthesis of the aglycon 1 was carried out by
reacting the sodium salt of cis-9-octadecenol with an-
hydrous 1,3-di-chlor-propan-2-ol. After purification,
the product was obtained in low yields (21%). In a
second attempt, epichlorhydrine was used instead,
but this did not increase the yield considerably. The
synthesis of compounds 2 and 3 was performed in a
similar way. The salt of the alcohol was reacted with
epichlorhydrine. The products were obtained in good
yields, after chromatographic purification. In case of
the synthesis of compounds 3, non-reacted alcohol
was nearly completely recovered.
Especially for physical characterisation and biologi-
caltesting, enoughsubstancehastobeprovided. There-
fore, a relative short-synthetic procedure is needed to
enable a rapid synthesis in good yields.
In recent years, Hato and co-workers prepared a new
class of glycolipids with a 1,3-di-O-alkyl-sn-glycerol
moiety. Mainly 1,3-dialkyl-glyco glycero lipids with n-
dodecyl and n-tetradecyl alkyl chains and oligomaltose
and cellobiose headgroups were synthesised in good to
excellent yields (Minamikawa et al., 1994) and a rel-
ative short-synthetic sequence. The lyotropic proper-
ties of the oligosaccharide headgroups were thoroughly
characterised (Hato, 2001; Hato and Minamikawa,
1996; Hato et al., 1998; Korchowiec et al., 2001). A
few examples with methyl branched phytanyl chains
can be found (Minamikawa and Hato, 1997). The am-
phiphilic properties of some of these compounds were
in part similar to those observed for the unsaturated
disaccharide compounds (Minden et al., 2002a).
From this observation, we synthesised a series
of 1,3-dialkyl-glyco-glycerolipids with disaccharide
(Maltose and Melibiose) and trisaccharide (mal-
totriose) headgroups. Different synthetic standard
routes were employed to ensure a fast and effi-
cient synthesis. To derive structure property relation-
ships, different types of alkyl chains were used: un-
saturated (cis-9-octadecenyl), saturated (n-tetradecyl)
and chiral methyl branched ((2R,4R,6R,8R)-2,4,6,8-
tetramethyldecyl). Additionally, a 1,2-diacyl-methyl
branched maltoside and unsaturated 1-O-alkyl mal-
totrioside were synthesised. Even in case of 1,3-ethers,
the unsaturated and methyl branched alkyl chains
should prevent crystallisation.
For the preparation of the dialkyl-glyco glycero
lipids, we used two different routes. As shown in Fig. 1,
the glycerol with octadecenyl chains was reacted us-
ing the trichloracetimidate procedure (Schmidt, 1986;
¨
Schmidt and Klager, 1985; Schmidt and Stumpp, 1983;
Schmidt et al., 1984), which has been proven to

G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
3
Fig. 1. Synthesis of 1,3-di-O-alkyl glyco glycero lipids via the trichloracetimidate route.

4
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
be useful in the preparation of glyco glycero lipids
(Minamikawa et al., 1994). We started with the un-
protected sugar, which was acetylated using acetic
acid anhydride in pyridine to give the products 5 and
11 in excellent yields. Next, the peracetylated sac-
charide was deprotected at the reducing terminus by
treatment with an excess of ammonium carbonate in
dimethylformamide at ambient temperature. Finally,
the glycosyl donors 7 and 13 were prepared by react-
ing trichloracetonitril in dichlormethane under basic
conditions. However, 1,8-diazabicyclo[5.4.0]undec-7-
en (DBU) was used as base (Schmidt and Kinzy, 1994),
instead of the often used sodium hydride (Schmidt and
Stumpp, 1983) or caesium carbonate. The great advan-
tage of this base is the change of colour during the
reaction, indicating at this point that sufficient amount
of base has been added. In the glycosylation coupling,
the glycosyl donor was reacted with 1,3-di-O-(cis-9-
octadecenyl)-glycerol 1 in the presence of trimethylsi-
lyl trifluormethanesulfonate (one-to-one molar ratio).
As reported by Minamikawa et al. (1994), the chem-
ical structure of the donors and the acceptors had no
Fig. 2. Synthesis of 1,3-di-O-alkyl glyco glycerol lipids via the ␤-peracetate.

G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
5
significant influence on the reaction, as can be seen
in the similar yields of the disaccharide and trisaccha-
ride product, respectively. Also the double bonds of the
glycerol were stable during the reaction. The peracety-
lated lipids 8 and 14 were deprotected using sodium
methoxide in anhydrous methanol to give the desired
products 9 and 15.
For the glycosylation reaction of the shorter-chained
aglycons (Fig. 2), which should be more reactive, we
used the standard procedure described by Vill et al.
(1989). Protection of the sugar was afforded by re-
action of the unprotected sugar in acetic acid anhy-
dride with a catalytic amount of sulfuric acid, yield-
ing the ␤-anomer in good yields. The ␤-peracetate
and the glycerols 2 and 3 were than reacted in anhy-
drous dichlormethane in the presence of boron trifluo-
ride etherate. Deprotection of the product was afforded
using sodium methoxide in anhydrous methanol. Al-
though this glycosylation reaction is more likely use-
ful for the preparation of alkyl glycosides, its use was
in this case successful and the overall yields are com-
parable to the trichloracetimidate procedure. However,
if the long-chained aglycon 1 was reacted with the ␤-
peracetate, product 8 was obtained only in poor yields.
This second synthetic route is therefore being useful if
glycerols with alkyl chains of medium-chain length are
used. In addition, the synthetic procedure is shorter by
two steps.
Fig. 3. Synthesis of 1,2-di-O-[(2ꢀꢀR,4ꢀꢀR,6ꢀꢀR,8ꢀꢀR)-2ꢀꢀ,4ꢀꢀ,6ꢀꢀ,8ꢀꢀ-tetramethyl-decanoyl]-4-O-(␣-d-glucopyranosyl)-␤-d-glucopyranoside.

6
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
For comparison, the corresponding 1,2-diacyl-
Due to their liquid crystallinity at ambient temper-
ature, the glycolipids 9, 15, 20, 27 and 29 could not be
recrystallised after the deprotection step. To ensure the
high purity, which is necessary for the exact determina-
tion of the liquid crystalline transition temperatures 9,
15 and 29 were purified by means of an additional gel
filtration, whereas for compounds 20 and 27, a subse-
quent silica gel chromatography was already success-
ful. The products 18 and 24 were purified by recrys-
tallisaton from methanol or propane-2-ol.
glycol glycerolipids and alkyl glycosides had to be
synthesised. The corresponding 1,2-di-O-oleoyl glyc-
erol maltoside was already synthesised by our group
(Minden et al., 2002a), but no data are available
on the corresponding 1,2-di-O-(2R,4R,6R,8R)-2,4,6,8-
tetramethyldecanoyl glycerol glycoside. The synthe-
sis of the 1,2-diacyl-glyco-glycero lipid 27 is partial
shown in Fig. 3. The diol 25 was synthesised simi-
lar to the well-elaborated procedure from Mannock et
al. (1987). The first step is a condensation of 1,2-di-
O-benzyl-sn-glycerol with maltoseperacetate in abs.
dichlormethane in the presence of boron trifluoride
etherate (Minden et al., 2002a; Vill et al., 1989) to ob-
tain the ␤-maltoside. It is again noteworthy that the eas-
ily accessible and optically pure 1,2-O-isopropylidene-
sn-glycerol racemises during the Koenigs–Knorr con-
densation procedure (Wehrli and Pomeranz, 1969;
Wickberg, 1958) or under Lewis acid catalysis, due
to intramolecular migration of the isopropylidene
group and cannot be used thus. After hydrogenolytic
removal of the benzyl protective groups of com-
pound, the glycerol 25 is afforded. This was ester-
ified with (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic
acid using the DCC method (Hassner and Alexa-
nian, 1978) and DMAP, yielding the ester 26. Af-
ter deacetylation under reductive conditions and a
subsequent chromatographic purification, the gly-
cosyl diacyl-glycerol 27 was obtained as a waxy
solid.
The alkyl glycoside 29 was synthesised according
to the method described by Vill et al. (1989). The ␤-
maltotriose peracetete was reacted under catalysis of
a lewis acid to give the desired alkly glycoside. In-
stead of tin tetrachloride, we used boron trifluoride
etherate as Lewis acid (Ferrier and Furneaux, 1976;
Minden et al., 2000) for the synthesis of the ␤-anomers.
The compound could be separated by simply silica gel
chromatography; no tedious ion-exchange chromatog-
raphy was necessary. After deprotection in anhydrous
methanol using catalytic amounts of sodium methoxide
the compound was obtained in high purity. Compared
to the synthesis of alkyl glycosides bearing monosac-
charide or disaccharide carbohydrate headgroups (see
3. Conclusions
Different standard synthetic procedures were em-
ployed to the synthesis of several glyco lipids. The
synthesised lipids are shown in Fig. 4. It was possi-
ble to obtain the lipids in short-synthetic steps in good
overall yields, partially in Gram-scale. On our knowl-
edge, we were the first to synthesise the 1,3-di-O-oleyl-
lipids 9 and 15, the oleyl-maltotrioside (29) and the chi-
ral methyl branched lipids 20 and 27. The 1,3-dialkyl-
glycerols were synthesised in a fast and efficient way.
For the glycosylation, two different routes were cho-
sen depending on the aglycon. The long-chained glyc-
erol bearing unsaturated alkyl chains was reacted with
the carbohydrate using the trichloracetimidate method.
The products were obtained in excellent yields for mal-
tose and maltotriose headgroups. The synthesis of the
medium and methyl branched glyco glycero lipids was
done using a shorter-reaction sequence was chosen.
The glycosylation of the ␤-peracetate using boron tri-
fluoride etherate as Lewis acid also afforded the desired
products. The yields were good for the preparation of
the n-tetradecyl lipids (35 and 45%) but the use of the
chiral methyl branched aglycon 3 led to lower yields.
For the synthesis of the glycosyl dialkyl-glycerols, it is
more likely to use the glycosylation via the peracety-
lated sugar. The reaction sequence is shortened by two
steps including tedious chromatographic purification
and the overall yields are comparable to that obtained
with the trichloracetimidate procedure. For the synthe-
sis of long-chain glycosyl dialkyl-glycerols and highly
methyl branched glycerols, the trichloracetimidate pro-
cedureissuperiortoothermethods. Anotherproblemin
the synthesis of biological interesting compounds is to
obtain compounds that show low-melting points. Due
to the need of liquid crystallinity at biological relevant
¨
for example, Bocker and Thiem, 1989; Minden et al.,
2000; Vill et al., 2000), compound 29 was obtained
only in poor yields. In this case, other methods should
be used for the preparation.

G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
7
Fig. 4. Structures of the synthesised lipids.
temperatures, the compounds cannot be recrystallised.
Therefore, more tedious chromatographic purification
steps are necessary to ensure highest purity of the
lipids.
␣-Melibiose monohydrate and maltotriose were
purchased from Acros Organics.
Thin-layer chromatography (TLC) was performed
on silica gel (Merck GF254), and detection was ef-
fected by spraying with a solution of ethanol:sulfuric
acid (9:1) followed by heating. Column chromatog-
raphy was performed using silica gel (Merck,
0.063–0.200 mm, 230–400 mesh). NMR spectra were
recorded on a Bruker AMX 400 or a Bruker DRX
5001 spectrometer (mc, centred multiplet; d, doublet;
t, triplet; dd, double doublet; dt, double triplet).
4. Experimental section
4.1. Materials and methods
Peracetylated disaccharides were prepared accor-
ding to the literature (Vill et al., 1989). Synthesis
of 3-O-[4ꢀ-O-(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,6ꢀꢀ-tetra-O-acetyl-␣-d-gluco-
pyranosyl-2ꢀ,3ꢀ,6ꢀ -tri-O-acetyl-␤-d-glucopyranosyl)-
sn-glycerol (25) has been described in an earlier
paper (Minden et al., 2002a). Synthesis of the chiral
fatty acid (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic
acid and the corresponding alcohol was performed
according to the procedure of Morr et al. (1992,
1997). n-Tetradecanol (purest grade) and maltose
monohydrate were purchased from Fluka Chemie.
4.2. Synthesis
Deacetylation (general procedure 1):
The compound was dissolved in anhydrous
methanol and sodium methoxide was added (pH 8–9).
The solution was stirred at ambient temperature until
TLC revealed the reaction to be complete. It was neu-
tralised then using Amberlyst IR 120 ion-exchanger
resign (protonated form), filtrated and evaporated in
vacuo.

8
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
4.2.1. 1,3-Di-O-[(2ꢀR,4ꢀR,6ꢀR,8ꢀR)-
magnesium sulphate and solvent was removed un-
der reduced pressure. The residue was purified by
short-column chromatography (light petroleum b.p.
50–70 ◦C–ethyl acetate 4:1).
2ꢀ,4ꢀ,6ꢀ,8ꢀ-tetra-methyl-decyl]-propan-2-ol (3)
The reaction was carried out as described for com-
pound 2, using 6 g (28 mmol) (2R,4R,6R,8R)-2,4,6,8-
tetramethyldecane-1-ol, 644 mg(28 mmol)sodiumand
1.3 g (1.1 mL; 14 mmol) epichlorhydrine in 100 mL of
toluene. The product was purified by column chro-
matography (light petroleum b.p. 50–70 ◦C–ethyl ac-
etate 20:1, then 9:1) to give slight yellow syrup.
Yield: 3.19 g (47%). C31H64O3 (484.4855).
Yield: 1.0 g (83%). C65H110O20 (1210.759).
1H NMR (500 MHz, CDCl3 + TMS): δ = 5.28–5.43
(m, 4H, H-olefin), 5.33 (d, 1H, H-1ꢀꢀ), 5.29 (dd, 1H,
H-3ꢀꢀ), 5.17 (dd, 1H, H-3ꢀꢀ), 4.98 (dd, 1H, H-4ꢀꢀ), 4.79
(dd, 1H, H-2ꢀꢀ), 4.72 (dd, 1H, H-2ꢀ), 4.71 (d, 1H, H-
1ꢀ), 4.40 (dd, 1H, H-6aꢀ), 4.19 (dd, 1H, H-6aꢀꢀ), 4.15
(dd, 1H, H.6bꢀ), 3.97 (dd, 1H, H-6bꢀꢀ), 3.90 (dd, 1H,
H-4ꢀ), 3.89 (ddd, 1H, H-5ꢀꢀ), 3.80–3.87 (m, 1H, H-
2), 3.59 (ddd, 1H, H-5ꢀ), 3.49 (d, 2H, H-1a, H-3a),
3.29–3.37 (m, 6H, H-1b, H-3b, ␣-CH2), 2.06, 2.03,
1.97, 1.95 (each s, 3H, OAc), 1.93 (s, 6H, OAc), 1.92 (s,
3H, OAc), 1.86–1.99 (m, 8H, H-allyl.), 1.40–1.53 (m,
4H, ␤-CH2), 1.12–1.33 (m, 44H, alkyl-CH2), 0.81 (t,
1H NMR (500 MHz, CDCl3 + TMS): δ = 3.84–3.90
(m, 1H, H-2), 3.34–3.44 (m, 8H, H-1a, H-1b, H-3a,
H-3b, H-1aꢀ, H-1bꢀ), 2.57 (m, 2H, H-2ꢀ), 1.78 (m,
2H, H-3aꢀ), 1.51–1.69 (m, 4H, H-4ꢀ, H-6ꢀ), 1.28–1.49
(m, 4H, H-8ꢀ, H-9aꢀ), 1.16–1.25 (m, 10H, H-5aꢀ,
H-7aꢀ, CH3-2ꢀ), 0.97–1.12 (m, 4H, H-3bꢀ, H-9bꢀ),
0.80–0.95 (m, 4H, H-5bꢀ, H-7bꢀ), 0.90 (d, 6H, CH3-
4ꢀ), 0.85 (t, 6H, CH3-10), 0.84 (m, 6H, CH3-8ꢀ), 0.81
(d, 6H, CH3-6ꢀ).
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
6H, alkyl-CH3); J1 ,2 = 8.6, J2 ,3 = 9.6, J3 ,4 = 9.6,
3
3
3
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J4 ,5 = 9.6, J5 ,6a = 2.8, J5 ,6b = 4.5, J6a ,b = 11.9,
3
3
3
13C NMR (125 MHz, CDCl3 + TMS): δ = 72.20 (C-
1, C-3), 76.50, 76.09 (C-1aꢀ, C-1bꢀ), 70.25 (C-2), 45.48,
44.88, 44.85 (C-5aꢀ, C-5bꢀ, C-7aꢀ, C-7bꢀ), 41.52, 41.30
(C-3aꢀ, C-3bꢀ), 31.58 (C-8aꢀ, C-8bꢀ), 31.08, 30.85 (C-
2aꢀ, C-2bꢀ), 28.94, 28.90 (C-9aꢀ, C-9bꢀ), 28.09, 28.05
(C-4aꢀ, C-4bꢀ), 27.25, 27.23 (C-6aꢀ, C-6bꢀ), 21.69,
21.65, 21.64, 21.59, 21.48, 21.45 (CH3-4aꢀ, CH3-4bꢀ,
CH3-6aꢀ, CH3-6bꢀ, CH3-8aꢀ, CH3-8bꢀ), 18.98 (CH3-
2aꢀ, CH3-2bꢀ), 11.25 (CH3-10aꢀ, CH3-10bꢀ).
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
J1 ,2 = 4.0, J2 ,3 = 9.8, J3 ,4 = 9.8, J4 ,5 = 9.8,
3
3
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ ꢀꢀ
J5 ,6a = 4.1, J5 ,6b = 2.0, J6a ,b = 12.5 Hz.
13C NMR (125 MHz, CDCl3 + TMS): δ = 170.55,
170.49, 170.27, 169.98, 169.60, 169.44 (C=O, OAc),
130.08 (C-olefin), 100.86, (C-1ꢀ), 96.06 (C-1ꢀꢀ), 78.70
(C-2), 75.88 (C-3ꢀ), 73.48 (C-4ꢀ), 72.92 (C-2ꢀ), 72.63
(C-5ꢀ), 71.86 (␣-CH2), 71.31 (C-1, C-3), 70.38 (C-2ꢀꢀ),
70.09 (C-3ꢀꢀ), 69.25 (C-5ꢀꢀ), 68.68 (C-4ꢀꢀ), 63.46 (C-
6ꢀ), 61.77 (C-6ꢀꢀ), 33.36 (C-allyl), 32.57, 30.51, 30.26,
30.04, 29.89, 29.79, 29.71, 26.62 (alkyl-CH2), 20.89,
20.78, 20.68, 20.64, 20.62, 20.60, 20.59 (CH3, OAc),
14.13 (alkyl-CH3).
4.2.2. 1,3-Di-O-[cis-9-octadecenyl]-2-O-[4ꢀ-O-
(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,6ꢀꢀ-tetra-O-acetyl-α-d-glucopyranosyl)-
2ꢀ,3ꢀ,6ꢀ-tri-O-acetyl-β-d-glucopyranosyl]-sn-
glycerol (8)
4.2.3. 1,3-Di-O-[cis-9-octadecenyl]-2-O-[4ꢀ-O-
(α-d-glucopyranosyl)-β-d-glucopyranosyl]-sn-
glycerol (9)
Nine hundred and eighty-eight milligrams
(0.815 mmol) 8 were deprotected using general
procedure 1. The product was purified by gel filtration
on a column of Serva LH-20 suspended in methanol.
Yield: 665 mg (89%). C51H96O13 (916.6851).
FAB-HIRESMS: m/z = 939.6712 [M + Na]+ (calc.
939.6749).
Seven hundred and eighty-one milligrams (1 mmol)
7, 593 mg (1 mmol) 1 and 100 mg of freshly dried
˚
powdered molecular sieve (4 A) were dissolved in
10 mL of anhydrous dichlormethane under an atmo-
sphere of nitrogen. Under cooling (0 ◦C), 222 mg
(1 mmol) trimethylsilyl trifluormethanesulfonate were
added dropwise. Afterwards, the reaction mixture was
stirred for 6 h at 0 ◦C. After TLC revealed the re-
action to be complete, pyridine was added, 50 mL
dichlormethane were added and the reaction mixture
was filtered through Celite®. The organic phase was
washed twice with 10 mL of a saturated solution of
sodium hydrogen carbonate, and subsequently with
10 mL of water. The organic phase was dried over
[α]2D0 = +22◦ (c = 0.17, MeOH)
1H NMR (400 MHz, d4-methanol): δ = 5.27–5.38
(m, 4H, H-olefin), 5.14 (d, 1H, H-1ꢀꢀ), 4.31 (d, 1H,
H-1ꢀ), 3.94–3.97 (m, 1H, H-2), 3.88 (dd, 1H, H-6aꢀ),
3.79–3.87 (m, 3H, H-4ꢀꢀ, H-6bꢀ, H-6aꢀꢀ), 3.65–3.73

G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
9
(m, 2H, H-5ꢀꢀ, H-6bꢀꢀ), 3.61 (m, 2H, H-3ꢀ, H-3ꢀꢀ),
3.56 (dd, 1H, H-4ꢀ), 3.43–3.50 (m, 3H, H-1a, H-
3a, H-2ꢀꢀ), 3.38 (ddd, 1H, H-5ꢀ), 3.24–3.29 (m,
3H, H-1b, H-3b, H-2ꢀ), 3.16–3.21 (m, 4H, alkyl-
␣-CH2), 1.92–2.05 (m, 8H, CH2-allyl.), 1.48–1.57
4.2.5. 1,3-Di-O-[cis-9-octadecenyl]-2-O-
{4ꢀ-O-[4ꢀꢀ-O-(α-d-glucopyranosyl)-α-d-
glucopyranosyl]-β-d-glucopyranosyl}-
sn-glycerol (15)
Nine hundred and seventy-five milligrams
(0.65 mmol) 14 were deprotected using general
procedure 1. The product was purified by gel filtration
on a column of Serva LH-20 suspended in methanol.
Yield: 647 mg (93%). C57H106O18 (1078.7379).
FAB-HIRESMS: m/z = 1101.7255 [M + Na]+ (calc.
1101.7277)
(m, 4H, alkyl-␤-CH2), 1.16–1.41 (m, 44H, alkyl-
CH2), 0.88 (t, 3H, alkyl-CH3); 3J1 ,2 = 8.1, J3 ,4 = 9.2,
3
ꢀ
ꢀ
ꢀ
ꢀ
3
3
3
3
2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J4 ,5 = 9.3, J5 ,6a = 2.1, J5 ,6b = 5.6, J6a ,b = 12.2,
ꢀꢀ ꢀꢀ
J1 ,2 = 3.6 Hz.
4.2.4. 1,3-Di-O-[cis-9-octadecenyl]-2-O-{4ꢀ-O-
[4ꢀꢀ-O-(2ꢀꢀꢀ,3ꢀꢀꢀ,4ꢀꢀꢀ,6ꢀꢀꢀ-tetra-O-acetyl-α-d-
[α]2D0 = +45◦ (c = 0.8, MeOH)
glucopyranosyl)-2ꢀꢀ,3ꢀꢀ,6ꢀꢀ-tri-O-acetyl-α-d-
1H NMR (500 MHz, d4-Methanol): δ = 5.26–5.36
(m, 4H, H-olefin), 5.12 (d, 1H, H-1ꢀꢀꢀ), 5.10 (d,
1H, H-1ꢀꢀ), 4.43 (d, 1H, H-1ꢀ), 3.92–3.98 (m, 1H,
H-2), 3.69–3.85 (m, 8H, H-4ꢀꢀ, H-4ꢀꢀꢀ, H-6aꢀ, H-
6aꢀꢀ, H-6aꢀꢀꢀ, H-6bꢀ, H-6bꢀꢀ, H-6bꢀꢀꢀ), 3.50–3.66 (m,
7H, H-1a, H-3a, H-3ꢀ, H-3ꢀꢀ, H-3ꢀꢀꢀ, H-5ꢀꢀ, H-5ꢀꢀꢀ),
3.42–3.49 (m, 7H, H-1b, H-3b, H-4ꢀ, alkyl-␣-CH2),
3.40 (dd, 2H, H-2ꢀꢀ, H-2ꢀꢀꢀ), 3.33 (mc, 1H, H-5),
3.20 (dd, 1H, H-2ꢀ), 1.91–2.04 (m, 8H, H-allyl.),
glucopyranosyl]-2ꢀ,3ꢀ,6ꢀ-tri-O-acetyl-β-d-
glucopyranosyl}-sn-glycerol (14)
The reaction was carried out as described for 8 using
1.1 g (1 mmol) 13 and 593 mg (1 mmol) 1. The product
was purified using light petroleum b.p. 50–70 ◦C–ethyl
acetate 1:1 as eluent.
Yield: 983 mg (70%). C77H126O28 (1498.8436).
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.25–5.26
(m, 6H, H-3ꢀꢀ, H-3ꢀꢀꢀ, H-olefin), 5.20 (d, 2H, H-1ꢀꢀ,
H-1ꢀꢀꢀ), 5.19 (dd, 1H, H-3ꢀ), 5.00 (dd, 1H, H-4ꢀꢀꢀ),
3.79 (dd, 1H, H-2ꢀꢀꢀ), 4.72 (d, 1H, H-1ꢀ), 4.71 (dd, 1H,
H-2ꢀ), 4.67 (dd, 1H, H-2ꢀꢀ), 4.35–4.42 (m, 2H, H-2,
H-6aꢀ), 3.80–4.27 (m, 11H, H-1a, H-3a, H-4ꢀ, H-4ꢀꢀ,
H-5ꢀꢀ, H-5ꢀꢀꢀ, H-6aꢀꢀ, H-6aꢀꢀꢀ, H-6bꢀ, H-6bꢀꢀ, H-6bꢀꢀꢀ),
3.45–3.51 (m, 2H, H-1b, H-3b), 3.30–3.38 (m, 5H,
H-5ꢀ, alkyl-␣-CH2), 2.09, 2.08, 2.03, 1.98, 1.97, 1.96,
1.95, 1.93, 1.92, 1.91 (each s, 3H, OAc), 1.44–1.51
(m, 8H, H-allyl.), 1.15–1.32 (m, 48H, alkꢀyl-CH2),
1.49–1.57 (m, 4H, ␤-CH2), 1.16–1.39 (m, 44H, alkyl-
CH2), 0.87 (t, 6H, alkyl-CH3); 3J1 ,2 = 8.1, J2 ,3 = 9.1,
3
ꢀ
ꢀ
ꢀ
ꢀ
3
3
3
= 4.1, 3J2
= 9.8,
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀꢀ,2ꢀꢀꢀ
ꢀꢀꢀ,3ꢀꢀꢀ
J1 ,2 = 4.1, J2 ,3 = 9.8, J1
3JCH ,CH = 6.6 Hz.
2
3
4.2.6. 1,3-Di-O-tetradecyl-2-O-[4ꢀ-O-(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,
6ꢀꢀ-tetra-O-acetyl-α-d-glucopyranosyl)-2ꢀ,3ꢀ,4ꢀ-tri-
O-acetyl-β-d-glucopyranosyl]-sn-glycerol (17)
3.39 g (5 mmol) Maltoseperacetate and 2.42 g
(5 mmol)
2 were dissolved in 50 mL of dry
3
ꢀ
3
0.81 (t, 6H, alkyl-CH3); J1 ,2ꢀ = 8.1, J2 ,3ꢀ = 9.2,
dichlormethane under an atmosphere of dry nitrogen.
994 mg (880 ␮L; 7 mmol) boron trifluoride etherate
were added and the solution was stirred for 6 h at am-
bient temperature until TLC revealed the reaction to
be complete. The reaction was quenched with 50 mL
of a saturated solution of sodium hydrogen carbonate,
the organic layer was separated and the aqueous layer
extracted twice with dichlormethane. The combined
organic phases were washed twice with water, dried
over magnesium sulphate and evaporated in vacuo. The
residue was purified by column chromatography (light
petroleum b.p. 50–70 ◦C–ethyl acetate 2:1).
J3 ,4ꢀ = 9.2, 3J1 ,2 = 3.8, J2 ,3 = 10.2, J1
= 3.8,
= 9.8,
3
ꢀ
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀꢀ,2ꢀꢀꢀ
ꢀꢀꢀ,5ꢀꢀꢀ
2J2
= 10.4,
3J3
= 9.8,
3J4
ꢀꢀꢀ,3ꢀꢀꢀ
ꢀꢀꢀ,4ꢀꢀꢀ
3JCH ,CH = 6.9 Hz.
2
3
13C NMR (100 MHz, CDCl3 + TMS): δ = 170.54,
170.52, 170.29, 170.27, 169.97, 169.83, 169.59, 169.43
(C=O, OAc), 130.34, 130.25 (C-olefin), 100.65 (C-1ꢀ),
96.14, 96.11 (C-1ꢀꢀ, C-1ꢀꢀꢀ), 78.76 (C-2), 75.88 (C-3ꢀ),
7ꢀ4.38 (C-3ꢀꢀ), 73.00, 72.87, 72.39, 72.11, 71.67 (C-
4 , C-4ꢀꢀ, C-5ꢀ, C-5ꢀꢀ, C-5ꢀꢀꢀ), 72.23, 72.19 (C-2ꢀ, C-
2ꢀꢀ), 70.92 (C-2ꢀꢀꢀ), 70.49, 70.46 (C-␣), 69.82 (C-3ꢀꢀꢀ),
69.34, 69.29 (C-1, C-3), 68.36 (C-4ꢀꢀꢀ), 63.50, 62.81,
61.83 (C-6ꢀ, C-6ꢀꢀ, C-6ꢀꢀꢀ), 33.02, 32.32, 30.19, 30.13,
30.08, 30.05, 29.93, 29.91, 29.72, 27.64, 26.55, 26.53,
23.09 (alkyl-CH2), 21.31, 21.28, 21.21, 21.08, 21.05,
20.99, 20.96 (CH3, OAc), 14.61, 14.58 (alkyl-CH3).
Yield: 3.00 g (54%). C57H98O20 (1102.6651).
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.34
(d, 1H, H-1ꢀꢀ), 5.29 (dd, 1H, H-3ꢀꢀ), 5.18 (t, 1H,
H-3ꢀ), 4.98 (t, 1H, H-4ꢀꢀ), 4.79 (dd, 1H, H-2ꢀꢀ),

10
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
4.74 (dd, 1H, H-2ꢀ), 4.70 (d, 1H, H-1ꢀ), 4.40 (dd,
1H, H-6aꢀ), 4.19 (dd, 1H, H-6aꢀꢀ), 4.15 (dd, 1H,
H-6bꢀ), 3.97 (dd, 1H, H-6bꢀꢀ), 3.91 (t, 1H, H-4ꢀ),
3.80–3.91 (m, 2H, H-2, H-5ꢀꢀ), 3.59 (ddd, 1H, H-5ꢀ),
3.44–3.51 (m, 2H, H-1a, H-3a), 3.29–3.38 (m, 6H,
H-1b, H-3b, alkyl-␣-CH2), 2.07, 2.03, 1.98, 1.96
(each s, 3H, OAc), 1.93 (s, 6H, OAc), 1.92 (s,
3H, OAc), 1.42–1.52 (m, 4H, ␤-CH2), 1.16–1.25
(m, 44H, alkyl-CH2), 0.81 (t, 6H, alkyl-CH3);
3
3
3
3
2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J4 ,5 = 9.1, J5 ,6a = 2.1, J5 ,6b = 5.7, J6a ,b = 12.1,
ꢀꢀ ꢀꢀ
J1 ,2 = 3.6 Hz.
4.2.8. 1,3-Di-O-[(2ꢀR,4ꢀR,6ꢀR,8ꢀR)-2ꢀ,4ꢀ,6ꢀ,8ꢀ-
tetramethyldecyl]-2-O-[4ꢀꢀ-O-(2ꢀꢀꢀ,3ꢀꢀꢀ,4ꢀꢀꢀ,6ꢀꢀꢀ-
tetra-O-acetyl-α-d-glucopyranosyl)-2ꢀꢀ,3ꢀꢀ,4ꢀꢀ-tri-
O-acetyl-β-d-glucopyranosyl]-sn-glycerol (19)
The reaction was carried out as described for
17 using 1.83 g (2.7 mmol) Maltoseperacetate, 1.3 g
(2.7 mmol) 3 and 537 mg (475 ␮L; 3.78 mmol) boron
trifluoride etherate. The product was purified using
light petroleum b.p. 50–70 ◦C–ethyl acetate 2:1 as elu-
ent.
3
3
3
3
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J1 ,2 = 8.1, J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7,
3
2
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
J5 ,6a = 2.8, J5 ,6b = 4.8, J6a ,6b = 12.2, J1 ,2 = 3.8,
3
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ
J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7, J5 ,6a = 4.1,
2
J5 ,6b = 2.3,
J6a ,6b = 12.9,
3JCH ,CH
=
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
2 3
Yield: 1.04 g (35%). C57H98O20 (1102.6651)
6.6 Hz.
1H NMR (500 MHz, CDCl3 + TMS): δ = 5.36 (d,
1H, H-1ꢀꢀꢀ), 5.28 (dd, 1H, H-3ꢀꢀꢀ), 5.21 (dd, 1H, H-3ꢀꢀ),
5.00 (t, 1H, H-4ꢀꢀꢀ), 4.85 (dd, 1H, H-2ꢀꢀꢀ), 4.76 (dd, 1H,
H-2ꢀꢀ), 4.74 (d, 1H, H-1ꢀꢀ), 4.41 (dd, 1H, H-6aꢀꢀ), 4.19
(dd, 1H, H-6aꢀꢀꢀ), 4.14 (dd, 1H, H-6bꢀꢀ), 3.96 (dd, 1H,
H-6bꢀꢀꢀ), 3.92 (t, 1H, H-4ꢀꢀ), 3.81–3.95 (m, 2H, H-2,
H-5ꢀꢀꢀ), 3.61 (ddd, 1H, H-5ꢀꢀ), 3.44–3.50 (m, 2H, H-1a,
H-3a), 3.28–3.40 (m, 6H, H-1b, H-3b, H-1aꢀ, H-1bꢀ),
2.56 (m, 2H, H-2ꢀ), 2.07, 2.03, 1.98, 1.96 (each s, 3H,
OAc), 1.94 (s, 6H, OAc), 1.91 (s, 3H, OAc), 1.78 (m,
2H, H-3aꢀ), 1.52–1.70 (m, 4H, H-4ꢀ, H-6ꢀ), 1.28–1.50
(m, 4H, H-8ꢀ, H-9aꢀ), 1.16–1.26 (m, 10H, H-5aꢀ, H-7aꢀ,
CH3-2ꢀ), 0.98–1.13 (m, 4H, H-3bꢀ, H-9bꢀ), 0.79–0.95
(m, 4H, H-5bꢀ, H-7bꢀ), 0.90 (d, 6H, CH3-4ꢀ), 0.85 (t,
6H, CH3-10ꢀ), 0.83 (m, 6H, CH3-8ꢀ), 0.79 (d, 6H, CH3-
13C NMR (100 MHz, CDCl3 + TMS): δ = 170.94,
170.87, 170.62, 170.34, 170.05, 169.82 (C=O, OAC),
100.66 (C-1ꢀꢀ), 95.94 (C-1ꢀ), 78.75 (C-2), 75.94
(C-3ꢀ), 73.25 (C-4ꢀ), 72.81 (C-2ꢀ), 72.43 (C-5ꢀ),
72.19, 72.10 (C-␣), 71.66, 70.92 (C-1, C-3), 70.40
(C-2ꢀꢀ), 70.09 (C-3ꢀꢀ), 69.80 (C-5ꢀꢀ), 68.47 (C-4ꢀꢀ),
63.33 (C-6ꢀ), 61.94 (C-6ꢀꢀ), 32.34, 30.12, 30.08,
29.95, 29.78, 26.56, 26.53, 23.11 (alkyl-CH2), 21.35,
21.25, 21.11, 21.06, 21.00 ( CH3, OAc), 14.54
(alkyl-CH3).
4.2.7. 1,3-Di-O-tetradecyl-2-O-[4ꢀ-O-(α-d-
glucopyranosyl)-β-d-glucopyranosyl]-sn-
glycerol (18)
2.98 g (2.70 mmol) 17 were deprotected using gen-
eral procedure 1. The product was recrystallised from
methanol.
3
3
3
3
6ꢀ).ꢀ J1 ,2 = 8.1, ꢀ J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3J5
= 2.8, 3J5
= 4.8, J6a ,6b = 12.2, J1 ,2 = 3.8,
2
3
,6aꢀ
,6bꢀ
ꢀꢀ ꢀꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
3
3
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ
J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7, J5 ,6a = 4.1,
Yield: 2.10 g (90%). C43H84O13 (808.5912).
3
2
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
J5 ,6b = 2.3, J6a ,6b = 12.9 Hz.
MALDITOF-MS: m/z = 831.6 [M + Na]+
13C NMR (100 MHz, CDCl3 + TMS): δ = 170.98,
Calc.
C 63.83
H 10.46
Found
C 63.92
H 10.58
170.90, 170.68, 170.34, 170.12, 169.92 (C=O, OAC),
100.54 (C-1ꢀꢀꢀ), 95.98 (C-1ꢀꢀ), 78.76 (C-2), 75.92 (C-
3ꢀꢀ), 73.26 (C-4ꢀꢀ), 72.81 (C-2ꢀꢀ), 72.43 (C-5ꢀꢀ), 72.25,
72.14 (C-1aꢀ, C-1bꢀ), 71.98, 71.05 (C-1, C-3), 70.48
(C-2ꢀꢀꢀ), 70.25 (C-3ꢀꢀꢀ), 69.78 (C-5ꢀꢀꢀ), 68.55 (C-4ꢀꢀꢀ),
63.42 (C-6ꢀꢀ), 61.98 (C-6ꢀꢀꢀ), 45.48, 44.87, 44.84 (C-
5aꢀ, C-5bꢀ, C-7aꢀ, C-7bꢀ), 41.51, 41.34 (C-3aꢀ, C-
3bꢀ), 31.57 (C-8aꢀ, C-8bꢀ), 31.07, 30.86 (C-2aꢀ, C-2bꢀ),
28.93, 28.89 (C-9aꢀ, C-9bꢀ), 28.07, 28.03 (C-4aꢀ, C-
4bꢀ), 27.26, 27.24 (C-6aꢀ, C-6bꢀ), 21.69, 21.65, 21.64,
21.59, 21.48, 21.45 (CH3-4aꢀ, CH3-4bꢀ, CH3-6aꢀ, CH3-
6bꢀ, CH3-8aꢀ, CH3-8bꢀ), 21.36, 21.26, 21.12, 21.07,
21.01 ( CH3, OAc), 18.98 (CH3-2aꢀ, CH3-2bꢀ), 11.25
(CH3-10aꢀ, CH3-10bꢀ).
[α]2D0 = +20◦ (c = 1.0, MeOH)
1H NMR (500 MHz, d4-Methanol): δ = 5.19 (d,
1H, H-1ꢀꢀ), 4.30 (d, 1H, H-1ꢀ), 3.94–3.96 (m, 1H,
H-2), 3.89 (dd, 1H, H-6aꢀ), 3.76–3.87 (m, 3H, H-
4ꢀꢀ, H-6bꢀ, H-6aꢀꢀ), 3.66–3.73 (m, 2H, H-5ꢀꢀ, H-
6bꢀꢀ), 3.58–3.63 (m, 2H, H-3ꢀ, H-3ꢀꢀ), 3.52 (dd, 1H,
H-4ꢀ), 3.43–3.50 (m, 3H, H-1a, H-3a, H-2ꢀꢀ), 3.39
(ddd, 1H, H-5ꢀ), 3.22–3.29 (m, 3H, H-1b, H-3b,
H-2ꢀ), 3.17–3.21 (m, 4H, alkyl-␣-CH2), 1.41–1.50
(m, 4H, alkyl-␤-CH2), 1.16–1.35 (m, 44H, alkyl-
CH2), 0.88 (t, 6H, alkyl-CH3); 3J1 ,2 = 8.1, J3 ,4 = 9.1,
3
ꢀ
ꢀ
ꢀ
ꢀ

G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
11
4.2.9. 1,3-Di-O-[(2ꢀR,4ꢀR,6ꢀR,8ꢀR)-2ꢀ,4ꢀ,6ꢀ,8ꢀ-
tetramethyldecyl]-2-O-[4ꢀꢀ-O-(α-d-glucopyr-
anosyl)-␤-d-glucopyranosyl]-sn-glycerol (20)
Nine hundred and fifty milligrams (0.86 mmol)
17 were deprotected using general procedure 1. The
product was purified by silica gel chromatography
(chloroform–methanol 10:1).
1.96, 1.93, 1.91 (each s, 3H, OAc), 1.43–1.51 (m,
4H, alkyl-␤-CH2), 1.14–1.28 (m, 44H, alkyl-CH2),
3
3
ꢀ
ꢀ
ꢀ
ꢀ
0.81 (t, 6H, alkyl-CH3); J1 ,2 = 7.9, J2 ,3 = 9.5,
3
3
3
3
2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J3 ,4 = 9.5, J4 ,5 = 9.7, J5 6a = 4.1, J6a ,b = 11.0,
3
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
J1 ,2 = 3.8, J2 ,3 = 10.7, J3 ,4 = 3.5, J4 ,5 = 1.0,
3JCH ,CH = 6.9 Hz.
2
3
13C NMR (125 MHz, CDCl3 + TMS): δ = 170.95,
170.77, 170.74, 170.58, 170.16, 169.76, 169.70 (C=O,
OAc), 100.94 (C-1ꢀ), 97.13 (C-1ꢀꢀ), 78.39 (C-2), 73.00
(C-3ꢀ), 72.17 (C-5ꢀ), 72.10, 71.92 (C-␣), 71.38 (C-2ꢀ),
71.70, 70.97 (C-1, C-3), 69.37 (C-4ꢀ), 68.36, 68.31 (C-
4ꢀꢀ, C-2ꢀꢀ), 67.85 (C-3ꢀꢀ), 66.85 (C-5ꢀꢀ), 66.83 (C-6ꢀ),
62.10 (C-6ꢀꢀ), 32.33, 30.12, 30.08, 29.96, 29.78, 26.58,
26.54, 23.10 (alkyl-CH2), 21.23, 21.12, 21.04, 20.80
( CH3, OAc), 14.53 (alkyl-CH3).
Yield: 522 mg (75%). C43H84O13 (808.5912).
MALDITOF-MS:
m/z = 831.5
[M + Na]+FAB-
HIRESMS: m/z = 831.5802 [M + Na]+ (calc. 831.581)
[α]2D0 = +25◦ (c = 0.2, MeOH)
1H NMR (500 MHz, d4-MeOH): d = 5.21 (d, 1H,
H-1ꢀꢀꢀ), 4.40 (d, 1H, H-1ꢀꢀ), 3.94–3.96 (m, 1H, H-2),
3.43–3.50 (m, 2H, H-1a, H-3a), 3.75–3.95 (m, 4H,
H-3ꢀꢀ, H-3ꢀꢀꢀ, H-4ꢀꢀ, H-4ꢀꢀꢀ) 3.52–3.70 (m, 6H, H-5ꢀꢀ,
H-5ꢀꢀꢀ, H-6aꢀꢀ, H-6aꢀꢀꢀ, H-6bꢀꢀ, H-6bꢀꢀꢀ), 3.48 (dd, 1H,
H-2ꢀꢀꢀ), 3.40 (dd, 1H, H-2ꢀꢀ), 3.22–3.29 (m, 6H, H-
1b, H-3b, H-1aꢀ, H.1aꢀ, H-1bꢀ, H-1bꢀ), 2.54–2.65 (m,
2H, H-2ꢀ, H-2ꢀ), 1.69–1.79 (m, 2H, H-3aꢀ, H-3aꢀ),
1.47–1.65 (m, 4H, H-4ꢀ, H-4ꢀ, H-6ꢀ, H-6ꢀ), 1.31–1.47
(m, 4H, H-8ꢀ, H-8ꢀ, H-9aꢀ, H-9aꢀ), 1.11–1.23 (m, 10H,
H-5aꢀ, H-5aꢀ, H-7aꢀ, H-7aꢀ, CH3-2ꢀ, CH3-2ꢀ), 1.01–1.11
(m, 4H, H-3bꢀ, H-3bꢀꢀ, H-9bꢀ, H-9bꢀ), 0.80–0.97 (m,
28H, H-5bꢀ, H-5bꢀ, H-7bꢀ, H-7bꢀ, CH3-4ꢀ, CH3-4ꢀ,
CH3-6ꢀ, CH3-6ꢀ, CH3-8ꢀ, CH3-8ꢀ, CH3-10ꢀ, CH3-
4.2.11. 1,3-Di-O-tetradecyl-2-O-[6ꢀ-O-(α-d-gala-
ctopyranosyl)-β-d-glucopyranosyl]-sn-
glycerol (24)
1.95 g (1.77 mmol) 23 were deprotected using gen-
eral procedure 1. The product was recrystallised from
2-propanol.
Yield: 1.27 g (89%). C43H84O13 (808.5912).
MALDITOF-MS: m/z = 831.5 [M + Na]+
Calc.
C 63.86
H 10.46
Found
C 63.91
H 10.10
[α]2D0 = +23◦ (c = 0.8, CH3COCH3)
10ꢀ); 3J1,2 = 9.7, 3J2,3 = 9.2, J1 ,2 = 4.1, J2 ,3 = 9.7,
2J␣a,a␤ = 12.2, 3J␣a,b-CH = 7.1, 3J␣␤,␤-CH = 7.6 Hz.
3
3
ꢀ
ꢀ
ꢀ
ꢀ
1H NMR (400 MHz, d4-methanol): δ = 4.89 (d, 1H,
H-1ꢀꢀ), 4.31 (d, 1H, H-1ꢀ), 4.01 (dd, 1H, H-6aꢀ),
3.90–3.95 (m, 2H, H-4ꢀꢀ, H-5ꢀꢀ, H-2), 3.69–3.80 (m,
5H, H-2ꢀꢀ, H-3ꢀꢀ, H-6aꢀꢀ, H-6bꢀ, H-6bꢀꢀ), 3.50 (ddd,
1H, H-5ꢀ), 3.43–3.49 (m, 3H, H-1a, H-3a, H-4ꢀ), 3.38
(dd, 1H, H-3ꢀ), 3.20–3.28 (m, 3H, H-1b, H-3b, H-
2ꢀ), 3.17–3.22 (m, 4H, alkyl-␣-CH2), 1.40–1.49 (m,
4H, ␤-CH2), 1.16–1ꢀ.36 (m, 44H, alkyl-CH2), 0.88 (t,
2
2
4.2.10. 1,3-Di-O-tetradecyl-2-O-[6ꢀ-O-(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,
6ꢀꢀ-tetra-O-acetyl-α-d-galactopyranosyl)-2ꢀ,3ꢀ,4ꢀ-
tri-O-acetyl-β-d-glucopyranosyl]-sn-glycerol (23)
The reaction was carried out as described for 17
using 2.95 g (4.3 mmol) Melibioseperacetate, 2.3 g
(4.3 mmol) 2 and 854 mg (760 ␮L; 6 mmol) boron tri-
fluoride etherate. The product was purified using light
petroleum b.p. 50–70 ◦C–ethyl acetate 2:1 as eluent.
Yield: 2.05 g (43%). C57H98O20 (1102.6651).
3
3
3
6H, alkyl-CH3); J1 ,2ꢀ = 8.1, J2 ,3 = 9.2, J3 ,4 = 9.2,
ꢀ
ꢀ
ꢀ
ꢀ
3
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
J4 ,5 = 9.2, J5 ,6a = 4.1, J5 ,6b = 2.0, J1 ,2 = 4.1 Hz.
1H NMR (500 MHz, CDCl3 + TMS): ␦ = 5.39 (dd,
1H, H-4ꢀꢀ), 5.27 (dd, 1H, H-3ꢀꢀ), 5.13 (t, 1H, H-3ꢀ),
5,09 (d, 1H, H-1ꢀꢀ), 5.05 (dd, 1H, H-2ꢀꢀ), 5.04 (dd,
1H, H-4ꢀ), 4.83 (dd, 1H, H-2ꢀ), 4.71 (d, 1H, H-1ꢀ),
4.15 (mc, 1H, H-5ꢀ), 4.00–4.08 (m, 2H, H-6aꢀꢀ, H-
6bꢀꢀ), 3.82–3.87 (m, 1H, H-2), 3.68 (dd, 1H, H-6aꢀ),
3.45–3.57 (m, 4H, H-1a, H-3a, H-5ꢀ, H-6bꢀ), 3.29–3.37
(m, 6H, H-1b, H-3b, alkyl-␣-CH2), 2.06, 1.98, 1.97,
4.2.12. 1,2-Di-O-[(2ꢀR,4ꢀR,6ꢀR,8ꢀR)-2ꢀ,4ꢀ,6ꢀꢀ,ꢀ8ꢀ ꢀ-
tetramethyldecanoyl]-3-O-[4ꢀꢀ-O-(2ꢀꢀꢀ,3ꢀꢀꢀ,4 ,6ꢀꢀꢀ-
tetra-O-acetyl-α-d-glucopyranosyl)-2ꢀꢀ,3ꢀꢀ,6ꢀꢀ-tri-
O-acetyl-β-d-glucopyranosyl]-sn-glycerol (26)
677.5 mg (0.95 mmol) 3-O-[4ꢀ-O-(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,6ꢀꢀ-tet-
ra-O-acetyl-␣-d-glucopyranosyl)-2,3,6-tri-O-acetyl-␤
-d-glucopyranosyl]-sn-glycerol (25), 435 mg (1.90
mmol)
(2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic

12
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
acid, 393 mg (1.90 mmol) N,Nꢀ-dicyclohexyl-
carbodiimide and a catalytic amount of 4-(1-
pyrrolidinyl)pyridine were dissolved in 25 mL of
dry dichlormethane and stirred at room temperature
overnight, until TLC revealed the reaction to be
complete. N, Nꢀ-dicyclohexylurea formed during the
course of the reaction was filtered off, the solvent
removed under reduced pressure and the resulting
syrup purified by silica gel chromatography (light
petroleum b.p. 50–70 ◦C–ethyl acetate 2:1).
4.2.13. 1,2-Di-O-[(2ꢀR,4ꢀR,6ꢀR,8ꢀR)-2ꢀ,4ꢀ,6ꢀ,8ꢀ-
tetramethyldecanoyl]-3-O-[4ꢀꢀ-O-(α-d-
glucopyranosyl)-β-d-glucopyranosyl]-
sn-glycerol (27)
Five hundred and eighteen milligrams (0.46 mmol)
26 were dissolved in a mixture of 7 mL dry methanol
and 3 mL dry dichlormethane. 0.18 mL (3.65 mmol)
hydrazine hydrate (100%) were added to this solu-
tion and the mixture was heated at the temperature
of reflux for 8 h. The solution was cooled in an ice-
bath, neutralised with formic acid and the solvent re-
moved in vacuo. The residue was submitted to chro-
matographic purification on silica gel (chloroform–
methanol 15:1).
Yield: 537 mg (49%). C57H94O22 (1130.6237).
1H NMR (500 MHz, CDCl3 + TMS): δ = 5.36 (d,
1H, H-1ꢀꢀꢀ), 5.30 (dd, 1H, H-3ꢀꢀꢀ), 5.20 (dd, 1H, H-
3ꢀꢀ), 5.00 (dd, 1H, H-4ꢀꢀꢀ), 5.16–5.23 (m, 1H, H-2),
4.81 (dd, 1H, H-2ꢀꢀꢀ), 4.78 (dd, 1H, H-2ꢀꢀ), 4.71 (d,
1H, H-1ꢀꢀ), 4.41 (dd, 1H, H-6aꢀꢀ), 4.32 (dd, 1H, H-
1a), 4.13–4.21 (m, 3H, H-1b, H-6bꢀꢀ, H-6aꢀꢀꢀ), 3.99
(dd, 1H, H-6bꢀꢀꢀ), 3.97 (dd, 1H, H-3a), 3.90 (t, 1H,
H-4ꢀꢀ), 3.85 (ddd, 1H, H-5ꢀꢀꢀ), 3.66 (dd, 1H, H-3b),
3.60 (ddd, 1H, H-5ꢀꢀ), 2.56 (mc, 2H, H-2’, H-2ꢀ),
2.08, 2.07, 2.00, 1.98 (each s, 3H, OAc), 1.94 (s, 6H,
OAc), 1.92 (s, 3H, OAc), 1.72–1.76 (m, 2H, H-3aꢀ,
H-3aꢀ), 1.54–1.65 (m, 2H, H-6ꢀ, H-6ꢀ), 1.48–1.54 (m,
2H, H-4ꢀ, H-4ꢀ), 1.30–1.46 (m, 4H, H-8ꢀ, H-8ꢀ, H-9aꢀ,
H-9aꢀ), 1.15–1.28 (m, 10H, H-5aꢀ, H-5aꢀ, H-7aꢀ, H-
7aꢀ, CH3-2ꢀ, CH3-2ꢀ), 0.95–1.09 (m 4H, H-3bꢀ, H-3bꢀ,
H-9bꢀ, H-9bꢀ), 0.80–0.94 (m, 28H, H-5bꢀ, H-5bꢀ, H-
7bꢀ, H-7bꢀ, CH3-4ꢀ, CH3-4ꢀ, CH3-6ꢀ, CH3-6ꢀ, CH3-8ꢀ,
Yield: 166 mg (43%). C43H80O15 (836.5497).
MALDITOF-MS: m/z = 859.4 [M + Na]+
FAB-HIRESMS: m/z = 859.5388 [M + Na]+ (calc.
859.5395)
[α]2D0 = +28◦(c = 0.3, MeOH)
1H NMR (500 MHz, d4-MeOH + TMS): δ = 5.27
(mc, 1H, H-2), 5.15 (d, 1H, H-1ꢀꢀꢀ), 4.40 (dd, 1H, H-
1a), 4.30 (d, 1H, H-1ꢀꢀ), 4.21 (dd, 1H, H-1b), 3.97
(dd, 1H, H-3a), 3.89 (dd, 1H, H-6aꢀꢀ), 3.79–3.86 (m,
2H, H-6bꢀꢀ, H-6aꢀꢀꢀ), 3.64–3.72 (m, 2H, H-5ꢀꢀꢀ, H-
6bꢀꢀꢀ), 3.62 (t, 2H, H-3ꢀꢀ, H-3ꢀꢀꢀ), 3.55 (dd, 1H, H-
4ꢀꢀ), 3.45 (dd, 1H, H-2ꢀꢀꢀ), 3.37 (ddd, 1H, H-5ꢀꢀ), 3.27
(dd, 1H, H-4ꢀꢀꢀ), 3.25 (dd, 1H, H-2ꢀꢀ), 2.53–2.64 (m,
2H, H-2ꢀ, H-2ꢀ), 1.68–1.78 (m, 2H, H-3aꢀ, H-3aꢀ),
1.46–1.64 (m, 4H, H-4ꢀ, H-4ꢀ, H-6ꢀ, H-6ꢀ), 1.30–1.46
(m, 4H, H-8ꢀ, H-8ꢀ, H-9aꢀ, H-9aꢀ), 1.10–1.22 (m,
10H, H-5aꢀ, H-5aꢀ, H-8aꢀ, H-8aꢀ, CH3-2ꢀ, CH3-
2ꢀ), 0.99–1.10 (m, 4H, H-3bꢀ, H-3bꢀ, H-9bꢀ, H-9bꢀ),
0.79–0.94 (m, 28H, H-5bꢀ, H-5bꢀ, H-7bꢀ, H-7bꢀ, CH3-
4ꢀ, CH3-4ꢀ, CH3-6ꢀ, CH3-6ꢀ, CH3-8ꢀ, CH3-8ꢀ, CH3-
3
3
CH3-8ꢀ, CH3-10ꢀ, CH3-10ꢀ); J1 ,2 = 8.1, J2 ,3 = 9.7,
ꢀ
ꢀ
ꢀ
ꢀ
3
2
3
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J3 ,4 = 9.7, J4 ,5 = 9.7, J5 ,6a = 2.8, J5 ,6b = 4.8,
3
3
3
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
J6a ,6b = 12.2, J1 ,2 = 3.8, J2 ,3 = 9.7, J3 ,4 = 9.7,
J4 ,5 = 9.7, J5 ,6a = 4.1, J5 ,6b = 2.3, J6a ,6b =
3
3
2
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
12.9 Hz.
13C NMR (125 MHz, CDCl3 + TMS): δ = 176.95,
176.01 (C-1ꢀ, C-1ꢀ), 170.95, 170.86, 170.65, 170.25,
169.37, 169.18 (C=O, OAc), 101.16 (C-1ꢀꢀꢀ), 96.01 (C-
1ꢀꢀ), 75.75 (C-3ꢀꢀ), 73.24 (C-4ꢀꢀ), 71.96 (C-2ꢀꢀ), 71.13
(C-5ꢀꢀ), 70.45 (C-2ꢀꢀꢀ), 70.11 (C-3ꢀꢀꢀ), 69.95 (C-5ꢀꢀꢀ),
69.65 (C-2), 68.33 (C-4ꢀꢀꢀ), 67.80 (C-3), 63.25 (C-
6ꢀꢀ), 62.14 (C-1), 61.85 (C-6ꢀꢀꢀ), 45.34, 44.86, 44.82
(C-5aꢀ, C-5bꢀ, C-7aꢀ, C-7bꢀ), 40.91, 40.81 (C-3aꢀ, C-
3bꢀ), 37.26, 37.17 (C-2aꢀ, C-2bꢀ), 31.53 (C-8aꢀ, C-8bꢀ),
28.98, 28.96 (C-9aꢀ, C-9bꢀ), 28.09, 28.06 (C-4aꢀ, C-
4bꢀ), 27.25 (C-6aꢀ, C-6bꢀ), 21.35, 21.26, 21.12, 20.99,
20.70, 20.68, 20.64, 20.59, 20.48, 20.45, 19.92, 19.90
(OAc, CH3-4aꢀ, CH3-4bꢀ, CH3-6aꢀ, CH3-6bꢀ, CH3-8aꢀ,
CH3-8bꢀ), 18.15(CH3-2aꢀ, CH3-2bꢀ), 11.20 (CH3-10aꢀ,
CH3-10bꢀ).
3
3
3
10ꢀ, CH3-10ꢀ); J1 ,2 = 7.9, J2 ,3 = 9.1, J3 ,4 = 9.1,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3
3
3
3
2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
J4 ,5 = 9.3, J5 ,6a = 1.9, J5 ,6b = 4.4, J6a3 ,6b = 12.3,
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
J1 ,2 = 3.8, J2 ,3 = 9.8, J3 ,4 = 9.2, J1a,2 = 2.8,
3J1b,2 = 6.6, J1a,1b = 12.0, J3a,2 = 5.4, J3b,2 = 6.0,
3
3
3
2J3a,3b = 11.0 Hz.
13C
NMR
(125 MHz,
d4-MeOH + TMS):
␦ = 177.03, 176.78 (C-1ꢀ, C-1ꢀ), 104.53 (C-1ꢀꢀ),
102.83 (C-1ꢀꢀꢀ), 81.10 (C-4ꢀꢀ), 77.44, 74.88 (C-3ꢀꢀ,
C-3ꢀꢀꢀ), 76.52 (C-5ꢀꢀ), 74.57 (C-5ꢀꢀꢀ), 74.30 (C-2ꢀꢀ),
73.95 (C-2ꢀꢀꢀ), 71.49 (C-2), 71.31 (C-4ꢀꢀꢀ), 68.71 (C-3),
63.85 (C-1), 62.64 (C-6ꢀꢀꢀ), 61.94 (C-6ꢀꢀ), 45.31, 44.85
(C-5aꢀ, C-5bꢀ, C-7aꢀ, C-7bꢀ), 40.89, 40.82 (C-3aꢀ,

G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
13
C-3bꢀ), 37.32, 37.27 (C-2aꢀ, C-2bꢀ), 31.52 (C-8aꢀ,
C-8bꢀ), 28.98 (C-9aꢀ, C-9bꢀ), 28.09 (C-4aꢀ, C-4bꢀ),
27.24 (C-6aꢀ, C-6bꢀ), 20.60, 20.64, 20.48, 20.46, 19.91
(CH3-4aꢀ, CH3-4bꢀ, CH3-6aꢀ, CH3-6bꢀ, CH3-8aꢀ,
CH3-8bꢀ),18.19, 18.14 (CH3-2aꢀ, CH3-2bꢀ), 11.20
(CH3-10aꢀ, CH3-10bꢀ).
13C NMR (125 MHz, CDCl3 + TMS): δ = 170.58,
170.56, 170.53, 170.31, 169.88, 169.63, 169.47 (C=O,
OAc), 130.38, 130.29 (C-olefin), 100.68 (C-1), 96.18,
96.15 (C-1ꢀ, C-1ꢀꢀ), 75.91 (C-3), 73.04 (C-4ꢀ), 72.91
(C-4ꢀ), 72.43 (C-2), 72.27 (C-3ꢀꢀ), 71.23 (C-5), 70.97
(C-2 ), 70.90 (C-␣), 70.53 (C-2ꢀꢀ), 70.50 (C-3ꢀ), 69.86
(C-5ꢀꢀ), 69.37 (C-5ꢀ), 69.33 (C-4ꢀ), 63.54 (C-6), 62.85
(C-6ꢀ), 61.87 (C-6ꢀꢀ), 31.95, 29.82, 29.56, 29.44, 29.36,
29.31, 27.26, 25.88, 22.73 (alkyl-CH2), 21.35, 21.32,
21.25, 21.12, 21.09, 21.03, 21.00 (CH3, OAc), 14.62
(alkyl-CH3).
4.2.14. (cis-9-Octadecenyl) 4-O-[4ꢀ-O-(2ꢀꢀ,3ꢀꢀ,4ꢀꢀ,
6ꢀꢀ-tetra-O-acetyl-α-d-glucopyranosyl)-2ꢀ,3ꢀ,6ꢀ-tri-
O-acetyl-α-d-glucopyranosyl]-2,3,6-tri-O-acetyl-
β-d-glucopyranoside (28)
4.23 g (4.4 mmol) ␤-d-Maltotrioseundecaacetate,
1.14 mL (1.34 g; 6.6 mmol) cis-9-octadecen-1-ol and
20 mg freshly dried powdered molecular sieve (0.4 nm)
were dissolved in 50 mL of dry dichlormethane under a
dry nitrogen atmosphere. 0.86 mL (679 mg; 6.8 mmol)
boron trifluoride etherate were added dropwise. After
5 h, TLC revealed the reaction to be complete. The re-
action was quenched with 50 mL of a saturated solution
of sodium hydrogen carbonate, the organic layer was
separated and the aqueous layer extracted twice with
dichlormethane. The combined organic phases were
washed twice with water, dried over magnesium sul-
phate and evaporated in vacuo. The resulting syrup was
purified by column chromatography (light petroleum
(b.p. 50–70 ◦C)–ethyl acetate 1:1).
Yield: 971 mg (19%). C56H86O26 (1174.5407).
1H NMR (500 MHz, CDCl3 + TMS): δ = 5.30–5.40
(m, 4H, H-3ꢀ, H-3ꢀꢀ, H-olefin), 5.25 (d, 2H, H-1ꢀ,
H-1ꢀꢀ), 5.22 (dd, 1H, H-3), 5.04 (dd, 1H, H-4ꢀꢀ,
4.83 (dd, 1H, H-2ꢀꢀ), 4.77 (dd, 1H, H-2), 4.71 (dd,
1H, H-2ꢀ), 4.48 (d, 1H, H-1), 4.41 (dd, 2H, H-6a,
H-6aꢀ), 4.29 (dd, 1H, H-6b), 4.21 (dd, 1H, H-6aꢀꢀ),
4.16 (dd, 1H, H-6bꢀ), 4.03 (dd, 1H, H-6bꢀꢀ), 3.97
(mc, 1H, H-5ꢀꢀ), 3.93 (dd, 1H, H-4ꢀ), 3.91 (mc, 1H,
H-5ꢀ), 3.90 (dd, 1H, H-4), 3.81 (dt, 1H, H-␣a), 3.67
(ddd, 1H, H-5), 3.40–3.45 (m, 1H, H-␣b), 2.10,
2.09, 2.03, 1.98, 1.96, 1.95, 1.93, 1.92 (each s, 3H,
OAc), 1.91 (s, 6H, OAc) 1.47–1.58 (m, 6H, H-allyl.,
␤-CH2), 1.17–1.38 (m, 22H, alkyl-CH2), 0.85 (t,
4.2.15. (cis-9-Octadecenyl) 4-O-[4ꢀ-O-(α-d-
glucopyranosyl)-α-d-glucopyranosyl]-β-d-
glucopyranoside (29)
Nine hundred and forty-two milligrams (0.8 mmol)
28 were deprotected using general procedure 1. The
product was purified by gel filtration on a column of
Serva LH-20 suspended in methanol.
Yield: 648 mg (98%). C36H66O16 (754.4351).
FAB-HIRESMS: m/z = 777.4248 [M + Na]+ (calc.
777.4279)
[α]2D0 = +40◦(c = 0.1, MeOH)
1H NMR (500 MHz, d4-methanol): d = 5.20–5.41
(m, 2H, H-olefin), 5.16 (d, 1H, H-1ꢀꢀ), 5.14 (d, 1H,
H-1ꢀ), 4.17 (d, 1H, H-1), 3.ꢀ78–3.91 (m, 6H, H-
3ꢀꢀ, H-6a, H-6aꢀ, H-6aꢀꢀ,H-6b , H.-6bꢀꢀ), 3.88 (dd,
1H, H-4ꢀꢀ), 3.76 (mc, 1H, H-5ꢀꢀ), 3.58–3.69 (m, 3H,
H-4ꢀ, H-5ꢀ, H-␣a), 3.61 (dd, 1H, H-4), 3.47–3.56
(m, 3H, H-3ꢀ, H-6b, H-␣b), 3.49 (dd, 1H, H-
2ꢀꢀ), 3.44 (dd, 1H, H-2ꢀ), 3.35 (mc, 1H, H-5),
3.27 (dd, 1H, H-3), 3.21 (dd, 1H, H-2), 1.95–2.06
(m, 4H, H-allyl.), 1.59–1.65 (m, 2H, ␤-CH2),
1.24–1.41 (m, 22H, alkyl-CH2), 0.90 (t, 3H, alkyl-
3
3
3
3
CH3); J1,2 = 8.1, J2,3 = 9.1, J3,4 = 9.3, J4,5 = 9.2,
3
3
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
J1 ,2 = 3.8, J2 ,3 = 9.8, J1 ,2 = 3.8, J2 ,3 = 9.8,
J4 ,5 = 9.8, JCH ,CH = 6.8 Hz.
3
ꢀꢀ ꢀꢀ
2
3
3H, alkyl-CH3); 3J1,2 = 8.1, J2,3 = 9.3, J3,4 = 9.2,
3
3
3J4,ꢀ5 = 9.2, 3J5,6ꢀ a = 2.4, 3J5,6b = 4.3, J6a,b = 12.1,
2
Acknowledgements
3J1ꢀ,2ꢀ = 4.1, J2ꢀ,3ꢀ = 10.4, J3 ,4ꢀ = 9.2, J4 ,5ꢀ = 9.2,
3
3
ꢀ
3
ꢀ
3J5
= 2.4, 3J5
= 3.8, J6a ,b = 12.1, J1 ,2 = 4.1,
2
3
We thank M. Duerkop and C. Brandt for technical
assistance. We are grateful to the Deutsche Forschungs-
gemeinschaft (SFB 470, Graduiertenkolleg 464) for fi-
nancial support.
,6aꢀ
,6bꢀ
ꢀꢀ ꢀꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
3
3
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ
J2 ,3 = 10.4, J3 2,4 = 9.8, J4 ,5 = 9.8, J5 ,6a = 3.5,
3
3J␣␤,␤-CH = 6.6,
ꢀꢀ
ꢀꢀ
ꢀꢀ ꢀꢀ
J5 ,6b = 2.2,
J6a ,b = 12.6,
2
2J␣a,b = 9.5, 3JCH ,CH = 6.6 Hz.
2
3

14
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
Minamikawa, H., Murakami, T., Hato, M., 1994. Synthesis of 1,3-di-
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