Thermotropic and lyotropic properties of long chain alkyl glycopyranosides: Part III: pH-sensitive headgroups

Article abstract of DOI:10.1016/j.chemphyslip.2003.09.007

As part of a series of papers, the influence of carbohydrate headgroups and aliphatic chains on the mesogenic properties of glycolipids was investigated. Alkyl glycosides with different types of aliphatic chains were synthesised. Neutral glycolipids were oxidized to their uronic acid derivatives, using the well established TEMPO-oxidation. For comparison a 6-deoxy-6-amino alkylglucopyranoside was synthesised. In addition, the thermotropic and lyotropic phase behaviour of the synthesised compounds were investigated. The thermotropism was characterised by polarising microscopy, the lyotropism by the contact preparation method.

Full text of DOI:10.1016/j.chemphyslip.2003.09.007

Chemistry and Physics of Lipids 127 (2004) 47–63
Thermotropic and lyotropic properties of long chain alkyl
glycopyranosides
Part III: pH-sensitive headgroups
G. Milkereita, M. Morrb, J. Thiema, V. Villa,∗
a
Institut für Organische Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
Gesellschaft für Biotechnologische Forschung mbH, Mascheroder Weg 1, 38124 Braunschweig, Germany
b
Received 20 May 2003; received in revised form 9 September 2003; accepted 10 September 2003
Abstract
As part of a series of papers, the influence of carbohydrate headgroups and aliphatic chains on the mesogenic properties of
glycolipids was investigated. Alkyl glycosides with different types of aliphatic chains were synthesised. Neutral glycolipids
were oxidized to their uronic acid derivatives, using the well established TEMPO-oxidation. For comparison a 6-deoxy-6-amino
alkylglucopyranoside was synthesised. In addition, the thermotropic and lyotropic phase behaviour of the synthesised compounds
were investigated. The thermotropism was characterised by polarising microscopy, the lyotropism by the contact preparation
method.
© 2003 Elsevier Ireland Ltd. All rights reserved.
Keywords: Alkyl glycopyranosides; Thermotropic liquid crystals; Lyotropic liquid crystals; Glycolipids; Uronic acids; Oxidation
1. Introduction
alkylated carbohydrates: while analysing the extracts
from tuberculosis bacteria R. Koch observed unusual
optical textures of their aqueous dispersions (Koch,
1884).
The driving force for the mesophase formation in
the case of amphiphilic molecules is a micro phase
separation leading to an aggregate structure with
separated regions for the lipophilic and hydrophilic
molecular moieties. This structure enables the main-
tenance of the van der Waals interaction in the hy-
drophobic region and of the more important hydrogen
bonding in the hydrophilic region, each stabilising
the formed mesophase.
The observation of a double melting of certain
long chain alkyl glucopyranosides, e.g. hexadecyl
␤-d-glucopyranoside (Fig. 1) by Fischer and Helferich
(1911) was the first indication of thermotropic liquid
crystalline properties in amphiphilic carbohydrates.
These amphotropic molecules form both ther-
motropic liquid crystalline phases in their pure state
upon heating and lyotropic liquid crystalline phases
upon addition of a solvent. The first observation
of lyotropic behaviour is also related to studies on
The principal phase behaviour of these compounds
is shown in Fig. 2 (Prade et al., 1995; Blunk et al.,
1998). A typical amphiphile is represented by a
∗
Corresponding author. Tel.: +49-40-42838-4269;
fax: +49-40-42838-4325.
E-mail address: vill@liqcryst.chemie.uni-hamburg.de (V. Vill).
0009-3084/$ – see front matter © 2003 Elsevier Ireland Ltd. All rights reserved.
doi:10.1016/j.chemphyslip.2003.09.007

48
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
Thiem, 1989; Vill et al., 1989; Boullanger, 1998).
These compounds dissolve in water, whereas the long
chain glycosides will only swell.
In previous papers, we focused our interest on
the influence of monosaccharide headgroups with
long alkyl chains as well as on a series of dodecyl
monoglucosides (Vill et al., 2000). In addition, a se-
ries of disaccharides was investigated by changing the
headgroup and the alkyl chain systematically (Minden
et al., 2000). We synthesised a series of glycoglyc-
erolipids with unsaturated and methyl branched fatty
acids (Minden et al., 2002a), and investigated the
influence of the monoalkylglycosides on membranes
by mixing with glycoglycerolipids (Minden et al.,
2002b).
To obtain glycolipids with switchable lyotropic
properties, we synthesised a series of pH-sensitive
alkyl glycosides starting with regular alkyl glyco-
sides. We used a different way to synthesise dodecyl
and tetradecyl glycosides and synthesised glycosides
with chiral and non chiral methyl branched alkyl
chains. Further their uronic acid derivatives and, to
accomplish the discussion in a previous paper (Vill
et al., 2000), a derivative of dodecyl monoglucoside
were synthesised.
Fig. 1. Hexadecyl ␤-d-glucopyranoside.
vertical line and usually exhibits only one mesophase,
but in the case of an unusual geometry of the hy-
drophilic headgroup polymorphism can occur. In this
case, cubic phases may also be observed (Fischer
et al., 1994), whereas simple amphiphiles such as
the one shown in Fig. 1 normally exhibit under ther-
motropic conditions only a SA phase (Jeffrey and
Wingert, 1992).
Deviation from the above-mentioned vertical line
may also be seen upon the addition of solvents, of
which the most common is water, because of its bi-
ological relevance. Whereas small amounts of water
will not change the phase type and transition temper-
atures, larger amounts will introduce new phases such
as cubic phases and columnar phases (HI/II) (Fairhurst
et al., 1998).
Even when the first observation of liquid crystalline
properties of alkyl glycosides was related to long chain
compounds, subsequent interest focused only on their
shorter chain counterparts (Jeffrey, 1984) because of
their interesting properties as surfactants (Böcker and
2. Results and discussion
2.1. Synthesis
T
For the synthesis of the alkyl glycosides we used
two different routes (Fig. 3). The synthesis of dodecyl
and tetradecyl gluco-respective galacto glycosides is
reported in the literature (Böcker and Thiem, 1989;
Vill et al., 1989; Noller and Rockwell, 1938; Weber
and Benning, 1982; Loewenstein et al., 1990; Tietze
et al., 1994). However, the yields were poor, due to
anomerisation and the problematic purification. Em-
ployed was the well established procedure by Vill
et al. (1989), however, boron trifluoride diethyl ether-
ate was used instead of tin tetrachloride. As reported,
by using this Lewis acid, the rate of anomerisa-
tion could be reduced (Ferrier and Furneaux, 1976;
Lindberg, 1948a,b). For purification silica gel was
successful, and no tedious ion exchange chromatog-
raphy was necessary. Thus, it was possible to obtain
the products in good yields. The synthesis of oleyl
Cub
bi
Cub
bi
Cub
Col
(H )
I
Col
(H
Sm
(L
Cub
dis
dis
A
)
)
II
α
H
O
Paraffin
2
Fig. 2. Principal phase behaviour of amphiphilic compounds (ther-
motropic: Col, columnar mesophase of normal or inverted type;
SmA, smectic A phase; Cubbi, bicontinuous cubic phase; ly-
otropic: Cubdis, discontinuous cubic phase; Cubbi, bicontinuous
cubic phase; HI, hexagonal phase; HII, inverted hexagonal phase;
L , lamellar phase).
␣

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
49
Fig. 3. Principal synthetic route for the preparation of alkyl ␤-d-glycopyranosides.
glycosides using the above-mentioned procedure was
reported in an earlier publication (Vill et al., 2000).
As reported, unsaturation in the aliphatic part low-
ers the melting point. Previously, we described some
glyco glycerol derivatives with chiral methyl branched
fatty acids, that showed melting points at ambient tem-
perature (Minden et al., 2002a), and other compounds
with this kind of chains were also reported (Morr
et al., 1997; Heppke et al., 1997). We used the chiral
alcohol (2R,4R,6R,8R)-2,4,6,8-tetramethyldecan-1-ol
which was synthesised using extracts from rump
glands of Anser a.f. domesticus (Morr et al., 1992;
Lindberg, 1948a). The alcohol and the acetobromo-
sugar were reacted with mercury salts using a vari-
ation of the Koenigs–Knorr glycosylation (Koenigs
and Knorr, 1901; Helferich and Weis, 1956).
Subsequently, a glycoside with a non chiral methyl
branched alkyl chain was synthesised. As alcohol
farnesol was employed and following hydrogenation,
resulted a mixture of the four possible diastereomeres
(McCarthy and Calvin, 1967; Nakajima et al., 1985;
Schouten et al., 1991). This mixture could not be

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G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
2.2. Mesogenic properties
2.2.1. Thermotropic properties
All compounds showed only SA phases in their pure
state according to the literature (Jeffrey and Wingert,
1992). The phases were characterised by their typical
anisotropic textures, Fig. 6 shows an example of the
observed SA phases. The transition temperatures of the
neutral alkyl glycosides are summarized in Table 1.
The clearing temperature—the temperature for the
phase transition between the crystalline or liquid crys-
talline phase to its isotropic phase—of alkyl glyco-
sides rises with increasing chain length, and reaches
a plateau where an optimal balance between the hy-
drophilic and hydrophobic part of the liquid crystal is
achieved, and drops afterwards slightly. In the case of
the monosaccharides this plateau is reached in an area
of 14–16 CH2 groups. In the case of the gluco deriva-
tives, 2 and 4, the clearing temperature of compound
4 is increased by ∼10 K, the optimum is in the area
between 14 and 16 CH2-groups. The diastereomeric
galacto compounds with an axial hydroxyl function
at C-4 are shorter than the gluco compounds, and
this optimal ratio should be reached earlier. Going
from compounds 18 (C-12 chain) to 20 (C-14 chain),
shows that the mesophase is only stabilised by 2 K.
The introduction of a double bond into the aliphatic
chain decreases the melting point in the case of both
diastereomers. Whereas compound 6 is already liquid
crystalline, compound 22 is still crystalline at am-
bient temperature. This indicates that the galactose
compounds built up a much more effective network
of hydrogen bondings than the glucose compounds.
As mentioned above we wanted to substitute the
unsaturated alkyl chains, to prevent the disadvantages
of double bonds, e.g. degradation by ␤-oxidation.
Looking at compound 8 shows that the melting point
lies at ambient temperature too, but the mesophase is
destabilised by 32.8 K, compared to glycoside 6. The
melting point of the galacto compound 24 is nearly at
ambient temperature, but the mesophase is stabilised
by 21.4 K compared to compound 22. This seems
to be surprising, but looking at the packing density
of this compound will give the answer. The gluco
compound 4 can build up a good hydrogen bonding
network of the sugar headgroups. The introduction of
a double bond into the aliphatic chain (compound 6)
has a dominant effect on the packing of the chains: the
Fig. 4. Principal synthetic route for the preparation of the uronic
acid and the triethylammonium salts.
separated and was reacted using the first synthetic
route, to give the product glycoside in a good yield.
The synthesis of the uronic acids was easy
and gave the desired products in good to excel-
lent yields (Fig. 4). Oxidation using the radical
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a
catalyst is very selective for the 6-position of the gly-
coside (Semmelhack et al., 1983; Davis and Flitsch,
1993; Inokuchi et al., 1990; Ma and Bobbit, 1991;
de Nooy et al., 1995; Györgydeák and Thiem, 1995).
Using this method, it was possible to oxidize even
compounds with unsaturated alkyl chains.
For opposite pH-behaviour a 6-deoxy-6-amino
alkylglycoside was synthesised (Fig. 5). Starting with
dodecyl-␤-d-glucopyranoside the monotosylate was
prepared (Cramer, 1963), the product treated with
sodium azide and the resulting 6-azidosugar reduced
with hydrogen in the presence of palladium on char-
coal as catalyst (Cron et al., 1958).

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
51
Fig. 5. Synthesis of dodecyl-6-deoxy-6-amino-␤-d-glucopyranoside.
possibility to build up hydrogen bonds is decreased,
which leads to the above mentioned effects. The pack-
ing of compound 8 is disturbed by the methyl substi-
tution in the aliphatic chain, but this is not as strong
as it would be expected for monophilic compounds.
Compound 22 shows that a double bond has less
effect on the packing than a methyl branched chain.
Despite this effects the mesophase of compound 24 is
stabilised, this means, that the disturbance of packing
and the hydrogen bonding network of the headgroup
are somewhat in balance.
Compound 10 shows a lower clearing temperature
than compound 8, which is surprising, because of
the higher number of methyl groups in compound 8.
Perhaps the homogenous stereochemistry in the alkyl
chain of compound 8 may facilitate the formation of
the mesophase. Some calamitic and discotic liquid
crystals were synthesised using this alcohol, these dis-
play very stable mesophases (Heppke et al., 1997).
The transition temperatures of the uronic acid alkyl
glycosides are summarized in Table 2. Apparently,
all melting points are only slightly higher compared
to the non oxidized analogues. Compound 12 exhibit
a higher clearing temperature than glycoside 2. The
higher intramolecular contrast, attributable to the car-
boxylic function, is responsible for this effect. The in-
tramolecular contrast is less strong for compound 25.
Due to the axial position at C-4 of the sugar moiety
the interaction is not as strong as for the glucuronides.
The clearing temperature of compound 25 is higher
than that of its analogue 18, but it rises not as high as
for compound 12.
For the tetradecyl glucuronide 13 and the tetradecyl
galacturonide 26, the effects are corresponding.
Investigating the remaining uronic acids was prob-
lematic. Compounds 14, 15, 16, 27 and 28 decom-
posed before reaching their clearing temperatures, or
decomposed near their clearing temperature. Looking
at the compounds with an unsaturation in the alkyl
chain, it was not unexpected, however, the low stabil-
ity of the compounds with the chiral methyl branched
chains was somehow surprising. Normally decompo-
sition occurs in the isotropic state, because the liquid
crystalline phase protects sensitive groups, like in a
crystal due to the dense packing a reaction is diffi-
cult. In the above-mentioned compounds, the packing
is less dense, this may favour a reaction.
The last compound we investigated was the dode-
cyl glucoside 31 in which the OH-group at C-6 of the
sugar moiety was substituted by an amino function.
In this case, the mesophase has nearly collapsed, it is
destabilised by 46.8 K compared to the original dode-
cyl glucoside 2. This shows clearly the importance of
the primary OH-group of the sugar headgroup. The
NH2 group is less polar, so it acts less efficiently in
the hydrogen network, whereas the carboxylic func-
tion is more polar than the OH-group and stabilises
the mesophase (Stangier et al., 1994).

52
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
Fig. 6. Polarisation micrograph—typical texture of a smectic A phase (here: dodecyl-␤-d-glucopyranoside): (a) SA-phase on heating; (b)
SA-phase forming on cooling from the isotropic phase.
2.2.2. Lyotropic properties
1991; Seddon, 1990; Seydel et al., 1993; Koynova and
Caffrey, 1994).
The lyotropism was investigated using the contact
preparation method (Van Doren and Wingert, 1994).
With this technique, a gradient of water concentration
is formed within the sample. This makes it possible to
show all phases ranging from the pure state without
water to the fully hydrated sample. General informa-
tion about the lyotropic structural polymorphism can
be found elsewhere (Luzzati et al., 1986; Israelachvili,
All neutral alkyl glycosides displayed in the con-
tact preparation with water only myelin figures, as
reported for compounds 6 and 22 (Vill et al., 2000)
and as expected for the other compounds (Table 3).
Myelins are mobile tubular structures which are con-
sidered to consist of cylindrical or helical arrangement
of many (300–5000) of the bilayers that constitute the

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
53
Table 1
Transition temperatures of alkyl monoglycosides
2
4
6
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
80.4
?
<20.0
<20.0
<20.0
99.4
102.1
80.6
25.9
SA
SA
SA
SA
SA
SA
SA
SA
SA
144.9
155.0
126.0
103.6
93.2
165.7
168.2
145.0
111.7
I (Focher et al., 1990)
I (Vill, 1990)
I (Vill et al., 2000)
I
8
10
18
20
22
24
I
I (Vill et al., 2000)
I (Hori and Ikegami, 1959)
I (Vill et al., 2000)
I
Cr, crystalline; SA, smectic A; I, isotropic melting; the transition temperatures are given in ◦C.
lamellar phase (Jeffrey and Wingert, 1992; Bouligand,
1998).
Then the triethylammonium salts of the uronic
acids were investigated, and this time it was possi-
ble to change the lyotropism. In the contact prepa-
ration with water, the salts of compounds 12, 13,
25, 26 and 27 showed the lamellar phase (L␣) and
on addition a broad columnar phase (HI). No cu-
bic phase was found between the lamellar and the
columnar phase. The glucuronic derivatives 14, 15,
16 and the galacturonic derivative 28 showed only a
very small columnar phase, depending on the alkyl
Investigating the uronic acids in the contact with wa-
ter led to similar results (Table 3). These compounds
are not acidic enough to form higher aggregates. So
it was not surprising that also compound 31 showed
only myelin figures in the contact.
We changed the solvent and contacted the uronic
acid derivatives with aqueous sodium hydroxide (5%),
but the results remained the same.

54
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
Table 2
Transition temperatures of alkyl monoglycosides with gylcopyranoside uronic acid and 6-deoxy-6-aminoglucopyranoside headgroups
12
13
14
15
16
25
26
27
28
31
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
Cr
83
90.1
31.2
<20.0
28.0
104
110.5
81.0
35.0
80.0
SA
SA
SA
SA
SA
SA
SA
SA
SA
SA
177
179
127
110
90
178.0
180.1
152
98
I (Vill et al., 1989)
I
Decomposition
Decomposition
Decomposition
I
I
Decomposition
Decomposition
I
95.2
The transition temperatures are given in ◦C.
chains that have the above-mentioned effects on the
packing.
2.3. Summary
The lyotropic phase behaviour can be changed by
variation of the pH. Especially the uronic acids dis-
played interesting phases in mixtures with tertiary and
quarterny amines.
Finally, we also changed the solvent in the contact
preparation with the glycoside 31. Instead of water we
used hydrochloric acid (5%), and were able to change
the lyotropism. In the contact this compound showed
a small columnar phase in addition to the lamellar
phase.
To prevent crystallisation alkyl glycosides were
synthesised using oleyl and methyl branched chains.

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
55
Table 3
the slide at the edge of the cover glass. As soon as
the solvent had moved under the cover glass and the
sample was completely surrounded with the solvent it
was placed again for some seconds on the hot stage at
a temperature of 100–120 ◦C and the phase behaviour
was investigated immediately afterwards by polarising
microscopy.
Phase sequences observed in the contact preparation of the syn-
thesised amphiphilic liquid crystals with: (a) water; (b) aqueous
sodium hydroxide (5%); (c) hydrochloric acid (5%)
Glycosides
Triethylammonium
salts of compound
∗,a
∗,a
∗,a
∗,a
∗,a
∗,a
∗,a
∗,a
∗,a
∗,a
c
∗,a,b
∗,a,b
∗,a,b
∗,a,b
∗,a,b
∗,a,b
∗,a,b
∗,a,b
∗,a,b
a
2
4
6
L
L
L
L
L
L
L
L
L
L
L
12
13
14
15
16
25
26
27
28
L
L
L
L
L
L
L
L
L
12
13
14
15
16
25
26
27
28
L
L
L
L
L
L
L
L
L
HI
HI
HI
HI
HI
HI
HI
HI
HI
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
␣
a
a
a
a
a
a
a
a
3.1.1. Synthesis
8
10
18
20
22
24
31
3.1.1.1. Glycosylation I (General procedure 1). The
peracetylated saccharide (10 mmol) and the alcohol
(15 mmol) were dissolved in 100 ml anhydrous methy-
lene chloride under an atmosphere of dry nitrogen,
and afterwards boron trifluoride etherate (14 mmol)
was added. The mixture was stirred 4–5 h at ambi-
ent temperature until TLC revealed the reaction to be
complete. After the reaction had been quenched with
100 ml of a saturated solution of sodium hydrogen car-
bonate, the organic layer was separated and the aque-
ous layer extracted two times with methylene chloride.
The combined organic phases were washed twice with
water (100 ml), dried over magnesium sulphate, fil-
trated and evaporated in vacuo. The resulting residue
was purified by column chromatography.
HI
(∗): Myelin figures in the contact preparation.
These compounds, except for the oleyl galactoside,
are liquid crystalline at or near ambient temperature.
The alkyl glycosides with the chiral methyl
branched chains are even more stable than the com-
pounds with unsaturated chains. The clearing temper-
ature of the chiral compounds is even higher than that
of the diastereomeric mixture.
3.1.1.2. Glycosylation II (General procedure 2). To
a solution of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecyl
alcohol (9.3 mmol), HgBr2 (5 mmol) and Hg(CN)2
(5 mmol) in 25 ml of dry acetonitrile was added under
nitrogen, over a period of 30 min at ambient temper-
ature, a solution of the acetobromo sugar (10 mmol)
in 25 ml of dry acetonitrile. When TLC revealed the
reaction to be complete, the mixture was concentrated
in vacuo, redissolved in 150 ml chloroform, filtered,
washed three times with 100 ml of a 1 M aqueous so-
lution of KBr and subsequently with 100 ml of water.
The organic phase was dried with MgSO4 and con-
centrated in vacuo to obtain a viscous residue which
was purified by column chromatography.
3. Experimental
3.1. Materials and methods
Thin-layer chromatography was performed on sil-
ica gel (Merck GF254), and detection was effected
by spraying with a solution of ethanol/sulphuric
acid (9:1), followed by heating. Column chromatog-
raphy was performed using silica gel 60 (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).
An Olympus BH optical polarising microscope
equipped with a Mettler FP 82 hot stage and a Mettler
FP 80 central processor was used to identify thermal
transitions and characterise anisotropic textures.
3.1.1.3. Deacetylation (General procedure 3). The
compound was dissolved in dry methanol and sodium
methoxide was added (pH 8–9). The solution was
stirred at ambient temperature until TLC revealed the
reaction to be complete, neutralised using Amberlyst
IR 120 ion-exchange resign (protonated form), fil-
trated and evaporated in vacuo.
For the contact preparation, a small amount of sam-
ple was placed on a microscope slide and covered with
a cover glass before heating to the SA phase. After-
wards a small amount of the solvent was placed on

56
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
1H NMR (400 MHz, d4-MeOH): δ = 4.30 (d, 1H,
H-1), 3.95 (dt, 1H, H-␣a), 3.93 (dd, 1H, H-6a), 3.70
(dd, 1H, H-6b), 3.58 (dt, 1H, H-␣b), 3.24–3.43 (m,
3H, H-3, H-4, H-5), 3.2 (dd, 1H, H-2), 1.67 (mc,
2H, ␤-CH2), 1.26–1.38 (m, 18H, –CH2–), 0.94 (t,
3.1.1.4. Oxidation (General procedure 4). The
compound was suspended in a saturated aqueous
solution of sodium hydrogen carbonate (6 ml). At a
temperature of 15 ◦C potassium bromide (12 mg) and
tetramethylpiperidine-1-oxyl (free radical) (11 mg)
were added. Seven millilitres of an aqueous solution
of sodium hypochlorite (14%) were added dropwise,
while temperature was kept strictly below 20 ◦C. The
reaction mixture was stirred at 15–20 ◦C until the
solution became clear. The reaction was diluted with
water (90 ml), adjusted to pH 2 with hydrochloric
acid (37%) and extracted four times with ethyl acetate
(25 ml). The combined organic phases where washed
twice with water (15 ml), dried over magnesium sul-
phate, filtrated and evaporated in vacuo. The residue
was coevaporated three times with ethyl acetate and
purified by column chromatography.
3
3
3
3H, alkyl-CH3); J1,2 = 8.1, J2,3 = 9.2, J5,6a
=
3
2
3
2.1, J5,6b = 5.5, J6a,b = 12.2, J␣a,␤-CH
=
2
3
2
7.0, J␣b,␤-CH = 6.6, J␣a,␣b = 9.7 Hz.
2
3.1.2.3. Tetradecyl-2,3,4,6-tetra-O-acetyl-␤-d-gluco-
pyranoside (3). Penta-O-acetyl-␤-d-glucopyranose
and tetradecyl alcohol were reacted using General
procedure 1. The product was purified by column
chromatography (light petroleum (50–70 ◦C)–ethyl
acetate 6:1). Yield: 1.70 g (31%).
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.20
(dd, 1H, H-3), 5.09 (dd, 1H, H-4), 4.98 (dd, 1H,
H-2), 4.49 (d, 1H, H-1), 4.27 (dd, 1H, H-6a), 4.14
(dd, 1H, H-6b), 3.87 (dt, 1H, H-␣a), 3.68 (ddd, 1H,
H-5), 3.46 (dt, 1H, H-␣b), 2.09, 2.04, 2.03, 2.01 (je
3.1.2. Preparation of triethylammonium salts
A small amount (0.02–0.08 mmol) of uronic acid
was dissolved in 1 ml of freshly distilled chloroform.
The solution was cooled to −5 ◦C and 1.1 eq. freshly
distilled triethylamine were added. After 10 min the
solvent was removed in vacuo. The residue was
washed two times with ice-cold n-hexane.
s, 3H, OAc), 1.51–1.62 (m, 2H, ␤-CH2), 1.22–1.35
3
(m, 22H, –CH2–), 0.88 (t, 3H, alkyl-CH3); J1,2
=
=
=
3
3
3
3
8.1, J2,3 = 9.7, J3,4 = 9.7, J4,5 = 9.7, J5,6a
3
2
3
4.6, J5,6b = 2.5, J6a,b = 12.2, J␣a,␤-CH
2
3
3
6.6, J␣b,␤-CH = 6.6, J␣a,␣b = 9.7 Hz.
2
3.1.2.4. Tetradecyl-β-d-glucopyranoside (4). 1.81 g
(3.32 mmol) 3 were deprotected using General proce-
dure 3. The product was purified by silica gel chro-
matography (chloroform–methanol 9:1). Yield: 1.21 g
(97%).
3.1.2.1. Dodecyl-2,3,4,6-tetra-O-acetyl-␤-d-gluco-
pyranoside (1). Penta-O-acetyl-␤-d-glucopyranose
and dodecyl alcohol were reacted using General
procedure 1. The product was purified by column
chromatography (light petroleum (50–70 ◦C)–ethyl
acetate 6:1). Yield: 2.44 g (48%).
1H NMR (400 MHz, d4-MeOH): δ = 4.27 (d, 1H,
H-1), 3.92 (dt, 1H, H-␣a), 3.88 (dd, 1H, H-6a), 3.69
(dd, 1H, H-6b), 3.55 (dt, 1H, H-␣b), 3.26–3.36 (m,
3H, H-3, H-4, H-5), 3.19 (dd, 1H, H-2), 1.64 (mc,
2H, ␤-CH2), 1.28–1.44 (m, 22H, –CH2–), 0.93 (t,
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.20
(dd, 1H, H-3), 5.09 (dd, 1H, H-4), 4.98 (dd, 1H,
H-2), 4.49 (d, 1H, H-1), 4.27 (dd, 1H, H-6a), 4.14
(dd, 1H, H-6b), 3.69 (ddd, 1H, H-5), 3.87 (dt, 1H,
H-␣a), 3.47 (dt, 1H, ␣b), 2.09, 2.04, 2.03, 2.01 (je
3
3
3
3H, alkyl-CH3); J1,2 = 8.1, J2,3 = 9.2, J5,6a
=
3
2
3
1.5, J5,6b = 5.1, J6a,b = 11.7, J
=
s, 3H, OAc), 1.52–1.62 (m, 2H, ␤-CH2), 1.22–1.33
a␣,␤-CH2
3
2
3
7.6, J
b␣,␤-CH2
= 6.6, Ja␣,b␣ = 9.7 Hz.
(m, 18H, –CH2–), 0.88 (t, 3H, alkyl-CH3); J1,2
=
=
=
3
3
3
3
8.1, J2,3 = 9.7, J3,4 = 9.7, J4,5 = 9.7, J5,6a
3.1.2.5. (cis-9ꢀ-Octadecenyl)-2,3,4,6-tetra-O-acetyl-
␤-d-glucopyranoside (5). Penta-O-acetyl-␤-d-glu-
copyranose and oleyl alcohol were reacted using Gen-
eral procedure 1. The product was purified by column
chromatography (light petroleum (50–70 ◦C)–ethyl
acetate 4:1). Yield: 2.69 g (45%).
3
2
3
4.6, J5,6b = 2.5, J6a,b = 12.2, J␣a,␤-CH
2
3
3
9.7, Jba,␤-CH = 9.7, J␣a,␣b = 9.7 Hz.
2
3.1.2.2. Dodecyl-β-d-glucopyranoside
(2). 2.3 g
(4.45 mmol) 1 were deprotected using General pro-
cedure 3. The product was purified by gel filtration
on a column of Serva LH-20 suspended in methanol.
Yield: 1.35 g (87%).
1H NMR (400 MHz, CDCl3+TMS): δ = 5.28–5.41
(m, 2H, H-olefinic), 5.21 (dd, 1H, H-3), 5.09 (dd,

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
57
3
3
1H, H-4), 4.99 (dd, 1H, H-2), 4.49 (d, 1H, H-1), 4.27
(dd, 1H, H-6a), 4.14 (dd, 1H, H-6b), 3.87 (dt, 1H,
H-␣a), 3.69 (ddd, 1H, H-5), 3.47 (dt, 1H, H-␣b),
2.09, 2.04, 2.03, 2.01 (je s, 12H, OAc), 1.96–2.05
(m, 4H, –CH2-allylic), 1.48–1.64 (m, 2H, ␤-CH2),
1.20–1.37 (m, 24H, –CH2–), 0.88 (t, 3H, alkyl-CH3);
JCH -␤,␤
=
6.6, JCH -␦,␦
=
6.6, JCH -␨,␨
=
3
3
33
3
6.5, JCH -␪,␪ = 6.1, Jalkyl-CH ,␫ = 6.6 Hz.
3
3
3.1.2.8. [(2R,4R,6R,8R)-2,4,6,8-Tetramethyldecyl]-
β-d-glucopyranoside (8). 1.8 g (3.30 mmol) 7 were
deprotected using General procedure 3. The product
was purified by gel filtration on a column of Serva
LH-20 suspended in methanol. Yield: 1.22 g (98%).
[α]2D0 = −32 (c = 0.1, methanol); C20H40O6
(376.2825); FAB: m/z = 399.5 (M + Na).
3J1,2 = 8.1, J2,3 = 9.7, J4,5 = 9.7, J5,6a
=
3
3
3
3
2
2
4.6, J5,6b
=
2.6, J6a,6b
=
12.2, J␣a,␣b
=
3
3
9.7, J␣a,␤-CH = 6.6, J␣b,␤-CH = 6.9 Hz.
2
2
3.1.2.6. (cis-9ꢀ-Octadecenyl)-␤-d-glucopyranoside
1H NMR (400 MHz, d4-MeOH): δ = 4.27 (d,
1H, H-1), 3.91 (dd, 1H, H-6a), 3.71 (dd, 1H, H-6b),
3.68 (dd, 1H, H-␣a), 3.48 (dd, 1H, H-␣b), 3.39 (dd,
1H, H-3), 3.27–3.36 (m, 2H, H-4, H-5), 3.22 (dd,
1H, H-2), 1.93 (mc, 1H, H-␤), 1.65 (mc, 2H, H-␦,
H-␨), 1.49 (mc, 1H, H-␪), 1.45 (mc, 1H, H-␫a), 1.41
(mc, 1H, H-␥a), 1.31 (mc, 1H, H-␩a), 1.27 (mc, 1H,
H-εa), 1.11 (mc, 1H, H-␫b), 0.99 (d, 3H, CH3-␤),
0.96 (mc, 1H, H-␥b), 0.94 (mc, 1H, H-εb), 0.93 (d,
3H, CH3-␦), 0.92 (t, 3H, alkyl-CH3), 0.92 (d, 3H,
CH3-␪), 0.90 (d, 3H, CH3-␨), 0.89 (mc, 1H, H-␩b);
(6). 3 g (5 mmol) 5 were deprotected using General
procedure 3. The product was purified by gel filtration
on a column of Serva LH-20 suspended in methanol.
Yield: 2.11 g (98%).
1H NMR (400 MHz, d4-MeOH): δ = 5.34–5.45
(m, 2H, H-olefinic), 4.28 (d, 1H, H-1), 3.94 (dt, 1H,
H-␣a), 3.90 (dd, 1H, H-6a), 3.70 (dd, 1H, H-6b), 3.57
(dt, 1H, H-␣b), 3.25–3.41 (m, 3H, H-3, H-4, H-5),
3.21 (dd, 1H, H-2), 1.97–2.13 (m, 4H, H-allylic), 1.66
(m, 2H, ␤-CH2), 1.28–1.47 (m, 24H, –CH2–), 0.94 (t,
3
3
3
3J1,2 = 8.1, J2,3 = 9.2, J3,4 = 9.2, J5,6a
=
3
3
3
3H, alkyl-CH3); J1,2 = 7.6, J2,3 = 9.2, J5,6a
=
3
2
2
3
2
3
3
2.0, J5,6b
=
5.6, J6a,6b
9.7, J␣a,␤-CH = 6.6, J␣b,␤-CH = 6.6 Hz.
=
12.2, J␣a,␣b
=
2.0, J5,6b = 5.1, J6a,b = 12.2, J␣a,␤ = 7.6,
3
3
2
3
3
J␣b,␤ = 5.1, J␣a,b = 9.2, JCH -␤,␤ = 6.6,
2
2
3
3
3
JCH -␦,␦
=
6.6, JCH -␨,␨
=
6.6, JCH -␪,␪
=
33
3
3
3.1.2.7. [(2R,4R,6R,8R)-2,4,6,8-Tetramethyldecyl]-2,
3,4,6-tetra-O-acetyl-␤-d-glucopyranoside (7). 2,3,4,
6-Tetra-O-acetyl-␣-d-glucopyranosyl bromide and
(2R,4R,6R,8R)-2,4,6,8-tetramethyldecyl alcohol were
reacted using General procedure 2. The prod-
uct was purified by column chromatography (light
petroleum (50–70 ◦C)–ethyl acetate 4:1). Yield: 1.90 g
(33%).
6.1, Jalkyl-CH ,␫ = 6.6 Hz.
3
3.1.2.9. 3,7,11-Trimethyldodecyl alcohol (9).
A
mixture of 10 g (44.9 mmol) 3,7,11-trimethyl-2,6,10-
dodecatrienyl alcohol (farnesol) and 0.3 g Pd/C (10%)
in 50 ml ethanol was stirred under 1 atm of hydro-
gen for 3 days. After TLC showed the reaction to
be complete, the catalyst was filtered off and the
solvent was removed in vacuo. The obtained oil was
purified by column chromatography (light petroleum
(50–70 ◦C)–ethyl acetate 6:1). Yield: 3.65 g (36%).
1H NMR (400 MHz, CDCl3+TMS): δ = 3.63–3.74
(m, 2H, H-␣a, H-␣b), 1.61 (mc, 1H, H-␤a), 1.57
(mc, 1H, H-␥), 1.51 (mc, 1H, H-␭), 1.39 (mc, 1H,
H-␤b), 1.36 (mc, 1H, H-␩), 1.16–1.33 (m, 8H, CH2-␦,
CH2-ε, CH2-␨, CH2-␪), 1.14 (mc, 2H, CH2-␹),
1.00–1.09 (m, 2H, CH2-␫), 0.89 (d, 3H, CH3-␥), 0.87
(d, 6H, CH3-␭, alkyl-CH3), 0.85 (d, 3H, CH3-␩);
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.21
(dd, 1H, H-3), 5.09 (dd, 1H, H-4), 5.00 (dd, 1H,
H-2), 4.47 (d, 1H, H-1), 4.26 (dd, 1H, H-6a), 4.14
(dd, 1H, H-6b), 4.12 (dd, 1H, H-␣a), 3.68 (ddd, 1H,
H-5), 3.64 (dd, 1H, H-␣b), 2.08, 2.04, 2.03, 2.01
(je s, 3H, OAc), 1.80 (mc, 1H, H-␤), 1.58 (mc, 1H,
H-␦), 1.57 (mc, 1H, H-␨), 1.42 (mc, 1H, H-␪), 1.37
(mc, 1H, H-␫a), 1.31 (mc, 1H, H-␥a), 1.22 (mc, 1H,
H-␩a), 1.20 (mc, 1H, H-εa), 1.04 (mc, 1H, H-␫b),
0.94 (d, 3H, CH3-␤), 0.86–0.91 (m, 2H, H-␥b,
H-εb), 0.87 (d, 3H, CH3-␦), 0.85 (t, 3H, alkyl-CH3),
0.82–0.85 (m, 1H, H-␩b), 0.84 (d, 3H, CH3-␪);
3JCH -␥,␥ = 6.6, JCH -␩,␩ = 6.6, JCH -␭,␭
=
3
3
3
3
3
3
6.6, Jalkyl-CH ,␭ = 6.6 Hz.
3
3J1,2 = 8.1, J2,3 = 9.7, J3,4 = 9.7, J4,5
=
3
3
3
3
3
2
3
9.7, J5,6a = 4.6, J5,6b = 2.6, J6a,b = 12.2,
3.1.2.10. (3,7,11-Trimethyldodecyl)-2,3,4,6-tetra-O-
acetyl-␤-d-glucopyranoside (10). Penta-O-acetyl-
3
2
3
J␣a,␤
=
6.6, J␣b,␤
=
5.0, J␣a,b
=
10.4,

58
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
␤-d-glucopyranose 1.0 g (4.38 mmol) and 3,7,11-
trimethyldodecyl alcohol 9 (1.12 g; 2.86 mmol) were
reacted using General procedure 1. The product was
purified by column chromatography (light petroleum
(50–70 ◦C)–ethyl acetate 4:1). Yield: 0.94 g (56%).
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.21
(dd, 1H, H-3), 5.09 (dd, 1H, H-4), 4.98 (dd, 1H, H-
2), 4.49 (d, 1H, H-1), 4.27 (dd, 1H, H-6a), 4.12 (dd,
1H, H-6b), 3.90 (mc, 1H, H-␣a), 3.69 (ddd, 1H, H-5),
3.51 (mc, 1H, H-␣b), 2.09, 2.04, 2.02, 2.01 (je s, 3H,
OAc), 1.61 (mc, 1H, H-␤a), 1.57 (mc, 1H, H-␥), 1.51
(mc, 1H, H-␭), 1.39 (mc, 1H, H-␤b), 1.36 (mc, 1H,
H-␩), 1.16–1.33 (m, 8H, CH2-␦, CH2-ε, CH2-␨, CH2-
␪), 1.14 (mc, 2H, CH2-␹), 1.00–1.09 (m, 2H, CH2-␫),
0.89 (d, 3H, CH3-␥), 0.87 (d, 6H, CH3-␭, alkyl-
3.50–3.60 (m, 2H, H-␣b, H-4), 3.40 (dd, 1H, H-3),
3.24 (dd, 1H, H-2), 1.6–1.68 (m, 2H, ␤-CH2), 1.25–
1.48 (m, 18H, –CH2–), 0.93 (t, 3H, alkyl-CH3);
3
3
3
3J1,2 = 7.6, J2,3 = 9.2, J3,4 = 9.7, J4,5
=
9.7 Hz.
3.1.2.13. Tetradecyl-β-d-glucopyranoside
uronic
acid (13). 0.2 g (0.53 mmol) 4 were reacted using
General procedure 4. The product was purified by sil-
ica gel chromatography (ethyl acetate, then methanol).
Yield: 0.18 g (89%).
[α]2D0 = −39.4 (c = 0.2, methanol); C20H40O6
(376.2825); calc. C 61.51, H 9.81; found C 61.73, H
9.88.
1H NMR (400 MHz, d4-MeOH): δ = 4.30 (d,
1H, H-1), 3.84–3.91 (m, 1H, H-␣a), 3.80 (d, 1H,
H-5), 3.50–3.61 (m, 2H, H-␣b, H-4), 3.39 (dd, 1H,
H-3), 3.26 (dd, 1H, H-2), 1.59–1.68 (m, 2H, ␤-CH2),
1.23–1.48 (m, 22H, –CH2–), 0.94 (t, 3H, alkyl-CH3);
3
3
CH3), 0.85 (d, 3H, CH3-␩); J1,2 = 8.1, J2,3
=
=
=
3
3
3
3
9.2, J3,4 = 9.7, J4,5 = 9.7, J5,6a = 4.6, J5,6b
2
3
3
2.6, J6a,b = 12.2, JCH −␥,␥ = 6.6, JCH −␩,␩
3
3
3
3
6.6, JCH −␭,␭ = 6.6, Jalkyl−CH ,␭ = 6.6 Hz.
3
3
3J1,2 = 8.1, J2,3 = 9.2, J3,4 = 9.7, J4,5
=
3
3
3
3.1.2.11. (3,7,11-Trimethyldodecyl)-β-d-gluco-
9.7 Hz.
pyranoside (11). 0.85 g (1.52 mmol) 10 were de-
protected using General procedure 3. The prod-
uct was purified by silica gel chromatography
(chloroform–methanol 9:1). Yield: 0.55 g (93%).
[α]2D0 = −34.4 (c = 0.2, methanol); C21H42O6
(390.2981); FAB: m/z = 413.2 (M + Na).
3.1.2.14. (cis-9ꢀ-Octadecenyl)-␤-d-glucopyranoside
uronic acid (14). 0.52 g (1.2 mmol) 6 were reacted
using General procedure 4. The product was puri-
fied by gel filtration on a column of Serva LH-20
suspended in methanol. Yield: 0.43 g (80%).
[α]2D0 = −20 (c = 0.3, methanol); C24H44O7
(444.3087); calc. C 64.84, H 9.97; found C 64.62, H
9.62.
1H NMR (500 MHz, d4-MeOH): δ = 4.24 (d,
1H, H-1), 3.95 (mc, 1H, H-␣a), 3.86 (dd, 1H,
H-6a), 3.67 (dd, 1H, H-6b), 3.56 (mc, 1H, H-␣b),
3.22–3.36 (m, 3H, H-3, H-4, H-5), 3.16 (dd, 1H,
H-2), 1.60 (mc, 1H, H-␤a), 1.57 (mc, 1H, H-␥),
1.51 (mc, 1H, H-␭), 1.38 (mc, 1H, H-␤b), 1.37
(mc, 1H, H-␩), 1.16–1.36 (m, 8H, CH2-␦, CH2-ε,
CH2-␨, CH2-␪), 1.14 (mc, 2H, CH2-␹), 1.00–1.09
(m, 2H, CH2-␫), 0.90 (d, 3H, CH3-␥), 0.88 (d,
6H, CH3-␭, alkyl-CH3), 0.85 (d, 3H, CH3-␩);
1H NMR (400 MHz, d4-MeOH): δ = 5.34–5.44
(m, 2H, H-olefinic), 4.29 (d, 1H, H-1), 3.94 (dt,
1H, H-␣a), 3.90 (d, 1H, H-5), 3.57 (dt, 1H, H-␣b),
3.27–3.40 (m, 2H, H-3, H-4), 3.20 (dd, 1H, H-2),
1.96–2.13 (m, 4H, H-allylic), 1.64 (m, 2H, ␤-CH2),
1.27–1.48 (m, 24H, –CH2–), 0.90 (t, 3H, alkyl-CH3);
3
3
2
3J1,2 = 7.6, J2,3 = 9.2, J4,5 = 9.7, J␣a,␣b
=
3
3
3
3
3
3J1,2 = 8.1, J2,3 = 9.2, J5,6a = 2.0, J5,6b
=
9.7, J␣a,␤-CH = 6.6, J␣b,␤-CH = 6.6 Hz.
2
2
2
3
3
5.1, J6a,b = 11.7, JCH -␥,␥ = 6.6, JCH -␩,␩
=
3
3
3
3
3.1.2.15. (3,7,11-Trimethyldodecyl)-β-d-gluco-
6.6, JCH -␭,␭ = 6.6, Jalkyl-CH ,␭ = 6.6 Hz.
3
3
pyranoside uronic acid (15). 50 mg (0.13 mmol) 11
were reacted using General procedure 4. The prod-
uct was purified by silica gel chromatography (ethyl
acetate, then methanol). Yield: 27 mg (54%).
3.1.2.12. Dodecyl-β-d-glucopyranoside uronic acid
(12). 0.3 g (0.86 mmol) 2 were reacted using Gen-
eral procedure 4. The product was purified by silica
gel chromatography (ethyl acetate, then methanol).
Yield: 0.23 g (73%).
[α]2D0 = −41 (c = 0.1, methanol); C21H40O7
(404.2774); FAB: m/z = 427.4 (M + Na).
1H NMR (400 MHz, d4-MeOH): δ = 4.29 (d,
1H, H-1), 3.95 (mc, 1H, H-␣a), 3.82 (d, 1H, H-5),
1H NMR (400 MHz, d4-MeOH): δ = 4.33 (d, 1H,
H-1), 3.84–3.91 (m, 1H, H-␣a), 3.80 (d, 1H, H-5),

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
59
3J1,2 = 8.1, J2,3 = 10.7, J3,4 = 3.6, J4,5
=
3
3
3
3.52–3.62 (m, 2H, H-4, H-␣b), 3.39 (dd, 1H, H-3),
3.16 (dd, 1H, H-2), 1.61 (mc, 1H, H-␤a), 1.57 (mc,
1H, H-␥), 1.53 (mc, 1H, H-␭), 1.39 (mc, 1H, H-␤b),
1.35 (mc, 1H, H-␩), 1.19–1.33 (m, 8H, CH2-␦,
CH2-ε, CH2-␨, CH2-␪), 1.14 (mc, 2H, CH2-␹),
1.01–1.09 (m, 2H, CH2-␫), 0.92 (d, 3H, CH3-␥), 0.89
(d, 6H, CH3-␭, alkyl-CH3), 0.86 (d, 3H, CH3-␩);
3
3
2
3
1.0, J5,6a = 6.6, J5,6b = 7.1, J6a,b = 11.2,
3
J␣a,␣b = 9.7, J␣b,␤-CH = 6.6 Hz.
2
3.1.2.18. Dodecyl-β-d-galactopyranoside
(18).
2.13 g (4.12 mmol) 17 were deprotected using Gen-
eral procedure 3. The product was purified by sil-
ica gel chromatography (chloroform–methanol 9:1).
Yield: 1.36 g (95%).
3J1,2 = 8.1, J2,3 = 9.2, J3,4 = 9.7, J4,5
=
3
3
3
3
3
3
9.7, JCH -␥,␥ = 6.6, JCH -␩,␩ = 6.6, JCH -␭,␭
=
3
3
3
3
6.6, Jalkyl-CH ,␭ = 6.6 Hz.
1H NMR (400 MHz, d4-MeOH): δ = 4.25 (d,
1H, H-1), 3.94 (dt, 1H, H-␣a), 3.87 (dd, 1H, H-4),
3.74–3.81 (m, 2H, H-6a, H-6b), 3.46–3.62 (m, 4H,
H-2, H-3, H-5, H-␣b), 1.62–1.70 (m, 2H, ␤-CH2),
1.28–1.47 (m, 18H, –CH2–), 0.94 (t, 3H, alkyl-CH3);
3
3.1.2.16. [(2R,4R,6R,8R)-2,4,6,8-Tetramethyldecyl]-
β-d-glucopyranoside uronic acid (16). 0.18 g
(0.48 mmol) 8 were reacted using General procedure
4. The product was purified by silica gel chromatog-
raphy (ethyl acetate, then methanol). Yield: 0.14 g
(73%).
3J1,2 = 7.1, J3,4 = 3.1, J4,5 = 1.0, J␣a,␤-CH
=
3
3
3
2
2
6.6, J␣a,␣b = 7.1 Hz.
[α]2D0 = −40 (c = 0.2, methanol); C20H38O7
(390.2618); calc. C 61.51, H 9.81; found C 61.40, H
9.71.
3.1.2.19. Tetradecyl-2,3,4,6-tetra-O-acetyl-␤-d-gala-
ctopyranoside (19). Penta-O-acetyl-␤-d-galacto-
pyranose and tetradecyl alcohol were reacted us-
ing General procedure 1. The product was puri-
fied by column chromatography (light petroleum
(50–70 ◦C)–ethyl acetate 6:1). Yield: 3.44 g (63%).
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.38
(dd, 1H, H-4), 5.21 (dd, 1H, H-2), 5.02 (dd, 1H,
H-3), 4.45 (d, 1H, H-1), 4.16 (dd, 1H, H-6a), 4.12
(dd, 1H, H-6b), 3.85–3.93 (m, 2H, H-5, H-␣a),
3.47 (dt, 1H, H-␣b), 2.15, 2.05, 2.04, 1.99 (je s,
1H NMR (400 MHz, d4-MeOH): δ = 4.32 (d, 1H,
H-1), 3.80 (d, 1H, H-5), 3.63 (dd, 1H, H-␣a), 3.56 (dd,
1H, H-4), 3.47 (dd, 1H, H-␣b), 3.41 (dd, 1H, H-3),
3.27 (dd, 1H, H-2), 1.93 (mc, 1H, H-␤), 1.65 (mc, 2H,
H-␦, H-␨), 1.49 (mc, 1H, H-␪), 1.45 (mc, 1H, H-␫a),
1.41 (mc, 1H, H-␥a), 1.31 (mc, 1H, H-␩a), 1.27 (mc,
1H, H-εa), 1.11 (mc, 1H, H-␫b), 0.99 (d, 3H, CH3-␤),
0.96 (mc, 1H, H-␥b), 0.94 (mc, 1H, H-εb), 0.93 (d, 3H,
CH3-␦), 0.92 (t, 3H, alkyl-CH3), 0.92 (d, 3H, CH3-␪),
3H, OAc), 1.53–1.63 (m, 2H, ␤-CH2), 1.20–1.36
3
0.90 (d, 3H, CH3-␨), 0.89 (mc, 1H, H-␩b); J1,2
=
=
=
=
3
(m, 22H, –CH2–), 0.88 (t, 3H, alkyl-CH3); J1,2
=
3
3
3
3
8.1, J2,3 = 9.2, J3,4 = 9.7, J4,5 = 9.7, J␣a,␤
3
3
3
3
8.1, J2,3 = 9.7, J3,4 = 3.6, J4,5 = 1.0, J5,6a
=
3
2
3
7.6, J␣b,␤
=
4.6, J␣a,b
=
9.2, JCH -␤,␤
3
3
2
5.1, J5,6b = 2.9, J6a,b = 11.4 Hz.
3
3
3
6.6, JCH -␦,␦ = 6.6, JCH -␨,␨ = 6.6, JCH -␪,␪
3
3
3
3
6.1, Jalkyl-CH ,␫ = 6.6 Hz.
3
3.1.2.20. Tetradecyl-β-d-galactopyranoside
(20).
3.33 g (6.11 mmol) 19 were deprotected using Gen-
eral procedure 3. The product was purified by silica
gel chromatography (chloroform–methanol 9:1) and
by gel filtration on a column of Serva LH-20 sus-
pended in methanol. Yield: 1.83 g (79%).
3.1.2.17. Dodecyl-2,3,4,6-tetra-O-acetyl-␤-d-galac-
topyranoside (17). Penta-O-acetyl-␤-d-galactopy-
ranose and dodecyl alcohol were reacted using Gen-
eral procedure 1. The product was purified by column
chromatography (light petroleum (50–70 ◦C)–ethyl
acetate 6:1). Yield: 2.28 g (44%).
[α]2D0 = −8.1 (c = 0.8, methanol); C20H40O6
(376.2825); calc. C 63.80, H 10.71; found C 61.41,
H 10.59.
1H NMR (400 MHz, CDCl3 + TMS): δ = 5.37
(dd, 1H, H-4), 5.20 (dd, 1H, H-2), 5.00 (dd, 1H,
H-3), 4.43 (d, 1H, H-1), 4.17 (dd, 1H, H-6a), 4.10
(dd, 1H, H-6b), 3.85–3.92 (m, 2H, H-5, H-␣a), 3.45
(dt, 1H, H-␣b), 2.13 (s, 3H, OAc), 2.03 (s, 6H, 2x
OAc), 1.97 (s, 3H, OAc), 1.50–1.64 (m, 2H, ␤-CH2),
1.20–1.36 (m, 18H, –CH2), 0.88 (t, 3H, alkyl-CH3);
1H NMR (400 MHz, d4-MeOH): δ = 4.23 (d,
1H, H-1), 3.92 (dt, 1H, H-␣a), 3.85 (dd, 1H, H-4),
3.74–3.77 (m, 2H, H-6a, H-6b), 3.49–3.59 (m, 3H,
H-␣b, H-2, H-5), 3.47 (dd, 1H, H-3), 1.64 (mc,
2H, ␤-CH2), 1.26–1.37 (m, 22H, –CH2–), 0.92 (t,

60
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
3
3
3
(m, 2H, H-5, H-6b), 3.66 (dd, 1H, H-␣a), 3.33 (dd,
1H, H-␣b), 2.15, 2.05, 2.04, 1.99 (je s, 3H, OAc),
1.81 (mc, 1H, H-␤), 1.59 (mc, 1H, H-␦), 1.56 (mc,
1H, H-␨), 1.41 (mc, 1H, H-␪), 1.37 (mc, 1H, H-␫a),
1.32 (mc, 1H, H-␥a), 1.21 (mc, 1H, H-␩a), 1.19 (mc,
1H, H-εa), 1.05 (mc, 1H, H-␫b), 0.93 (d, 3H, CH3-␤),
0.90 (mc, 1H, H-␥b), 0.88 (mc, 1H, H-εb), 0.87 (d,
3H, CH3-␦), 0.85 (t, 3H, alkyl-CH3), 0.82–0.84 (m,
1H, H-␩b), 0.84 (d, 3H, CH3-␪), 0.83 (d, 3H, CH3-␨);
3H, alkyl-CH3); J1,2 = 7.4, J2,3 = 9.7, J3,4
=
=
3
3
2
3.6, J4,5
=
1.0, J␣a,␤-CH
=
6.6, J␣a,␣b
2
9.7 Hz.
3.1.2.21. (cis-9ꢀ-Octadecenyl)-2,3,4,6-tetra-O-acetyl-
␤-d-galactopyranoside (21). Penta-O-acetyl-␤-d-
galactopyranose and oleyl alcohol were reacted us-
ing General procedure 1. The product was puri-
fied by column chromatography (light petroleum
(50–70 ◦C)–ethyl acetate 4:1). Yield: 3.53 g
(59%).
3J1,2 = 8.1, J2,3 = 10.2, J3,4 = 3.1, J4,5
=
3
3
3
3
2
3
3
1.0, J5,6a = 6.1, J6a,b = 11.2, J␣a,␤ = 6.6,
2
3
3
1H NMR (400 MHz, CDCl3 +TMS): δ = 5.39 (dd,
1H, H-4), 5.28–5.36 (m, 2H, H-olefinic), 5.20 (dd,
1H, H-2), 5.00 (dd, 1H, H-3), 4.45 (d, 1H, H-1), 4.19
(dd, 1H, H-6a), 4.12 (dd, 1H, H-6b), 3.84–3.94 (m,
2H, H-5, H-␣a), 3.47 (dt, 1H, H-␣b), 2.16 (s, 2H,
OAc), 2.05 (s, 6H, OAc), 1.99 (s, 3H, OAc), 1.92–2.08
(m, 4H, –CH2-allylic), 1.48–1.62 (m, 2H, ␤-CH2),
1.20–1.38 (m, 22H, –CH2–), 0.88 (t, 3H, alkyl-CH3);
J␣b,␤ = 5.1, J␣a,b = 9.2, JCH -␤,␤ = 6.6,
3
3
3
JCH -␦,␦
=
6.6, JCH -␨,␨
=
6.5, JCH -␪,␪
=
33
3
3
6.2, Jalkyl-CH ,␫ = 7.1 Hz.
3
3.1.2.24. [(2R,4R,6R,8R)-2ꢀ,4ꢀ,6ꢀ,8ꢀ-Tetramethyldec-
yl]-β-d-galactopyranoside (24). 1.31 g (2.41 mmol)
23 were deprotected using General procedure 3. The
product was purified by gel filtration on a column of
Serva LH-20 suspended in methanol. Yield: 0.83 g
(92%).
3J1,2 = 8.1, J2,3 = 10.2, J3,4 = 3.1, J4,5
=
3
3
3
3
3
2
3
1.0, J5,6a = 6.6, J5,6b = 7.1, J6a,b = 11.2,
[α]2D0 = −21.9 (c = 0.3, methanol); C20H40O6
(376.2825); calc. C 63.80, H 10.71; found C 63.12, H
9.65.
2
J␣b,␤-CH = 6.6, J␣a,␣b = 9.7 Hz.
2
3.1.2.22. (cis-9ꢀ-Octadecenyl)-␤-d-galactopyranoside
(22). 3.5 g (5.89 mmol) 21 were deprotected using
General procedure 3. Yield: 2.46 g (97%).
1H NMR (400 MHz, d4-MeOH): δ = 4.23 (d,
1H, H-1), 3.87 (dd, 1H, H-4), 3.73–3.81 (m, 2H,
H-6a, H-6b), 3.65 (dd, 1H, H-2), 3.56 (dd, 1H,
H-␣a), 3.45–3.54 (m, 3H, H-␣b, H-3, H-5), 1.93
(mc, 1H, H-␤), 1.65 (mc, 1H, H-␦), 1.63 (mc, 1H,
H-␨), 1.49 (mc, 1H, H-␪), 1.44 (mc, 1H, H-␫a),
1.39 (mc, 1H, H-␥a), 1.31 (mc, 1H, H-␩a), 1.25
(mc, 1H, H-εa), 1.11 (mc, 1H, H-␫b), 0.99 (d, 3H,
CH3-␤), 0.92–0.97 (m, 2H, H-␥b, H-εb), 0.92 (d, 3H,
CH3-␦), 0.91 (t, 3H, alkyl-CH3), 0.90 (d, 3H, CH3-␪),
0.89 (d, 3H, CH3-␨), 0.84–0.89 (m, 1H, H-␩b);
1H NMR (400 MHz, d4-MeOH): δ = 5.27–5.46
(m, 2H, H-olefinic), 4.23 (d, 1H, H-1), 3.93 (dt,
1H, H-␣a), 3.87 (dd, 1H, H-4), 3.78 (dd, 1H, H-6a),
3.76 (dd, 1H, H-6b), 3.5–3.70 (m, 3H, H-2, H-5,
H-␣b), 3.49 (dd, 1H, H-3), 1.96–2.13 (m, 4H,
H-allylic), 1.59–1.69 (m, 2H, ␤-CH2), 1.27–1.45
3
(m, 30H, –CH2–), 0.94 (t, 3H, alkyl-CH3); J1,2
=
=
=
3
3
3
3
7.1, J2,3 = 9.7, J3,4 = 3.1, J4,5 = 1.0, J5,6a
3
2
3
6.6, J5,6b = 5.5, J6a,b = 11.5, J␣a,␤-CH
2
3
3
3
3J1,2 = 8.1, J2,3 = 9.7, J3,4 = 3.6, J4,5
=
=
=
2
6.6, J␣a,␣b = 9.7 Hz.
3
2
3
1.0, J␣a,␤
=
7.6, J␣a,b
=
9.7, JCH -␤,␤
3
3
3
3
6.6, JCH -␦,␦ = 6.6, JCH -␨,␨ = 6.1, JCH -␪,␪
3.1.2.23. [(2R,4R,6R,8R)-2,4,6,8-Tetramethyldecyl]-
2,3,4,6-tetra-O-acetyl-␤-d-galactopyranoside (23).
2,3,4,6-Tetra-O-acetyl-␣-d-galactopyranosyl bromide
and (2R,4R,6R,8R)-2,4,6,8-tetramethyldecyl alcohol
were reacted using General procedure 2. The result-
ing syrup was purified by silica gel chromatography
(light petroleum (50–70 ◦C)–ethyl acetate 4:1). Yield:
2.45 g (46%).
3
3
3
3
6.6, Jalkyl-CH ,␫ = 6.6 Hz.
3
3.1.2.25. Dodecyl-β-d-galactopyranoside uronic acid
(25). 0.3 g (0.86 mmol) 18 were reacted using Gen-
eral procedure 4. The product was purified by silica gel
chromatography (ethyl acetate, then methanol). Yield:
0.21 g (67%).
[α]2D0 = −19.6 (c = 0.2, methanol); C18H34O7
(362.2305); calc. C 59.65, H 9.45; found C 59.61, H
9.72.
1H NMR (400 MHz, CDCl3 +TMS): δ = 5.38 (dd,
1H, H-4), 5.21 (dd, 1H, H-2), 5.02 (dd, 1H, H-3),
4.43 (d, 1H, H-1), 4.19 (dd, 1H, H-6a), 4.09–4.16

G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
61
1H NMR (400 MHz, d4-MeOH): δ = 4.29 (d,
1H, H-1), 3.85 (dt, 1H, H-␣a), 3.79 (d, 1H, H-5),
3.43–3.55 (m, 2H, H-4, H-␣b), 3.38 (t, 1H, H-3),
3.22 (dd, 1H, H-2), 1.57–1.63 (m, 2H, ␤-CH2),
[α]2D0 = −31 (c = 0.1, methanol); C20H38O7
(390.2618); calc. C 61.51, H 9.81; found C 61.63, H
9.45.
1H NMR (400 MHz, d4-MeOH): δ = 4.27 (d,
1H, H-1), 3.90 (d, 1H, H-5), 3.88 (dd, 1H, H-4),
3.49–3.68 (m, 4H, H-2, H-3, H-␣a, H-␣b), 1.94
(mc, 1H, H-␤), 1.65 (mc, 1H, H-␦), 1.62 (mc, 1H,
H-␨), 1.49 (mc, 1H, H-␪), 1.44 (mc, 1H, H-␫a),
1.36 (mc, 1H, H-␥a), 1.32 (mc, 1H, H-␩a), 1.25
(mc, 1H, H-εa), 1.12 (mc, 1H, H-␫b), 1.00 (d, 3H,
CH3-␤), 0.92–0.97 (m, 2H, H-␥b, H-εb), 0.92 (d, 3H,
CH3-␦), 0.91 (t, 3H, alkyl-CH3), 0.90 (d, 3H, CH3-␪),
0.89 (d, 3H, CH3-␨), 0.85–0.88 (m, 1H, H-␩b);
1.25–1.47 (m, 18H, –CH2–), 0.89 (t, 3H, alkyl-CH3);
3
3
3
3J1,2 = 8.1, J2,3 = 9.2, J3,4 = 3.6, J4,5
=
3
3
1.5, J␣a,-CH = 6.6, J␣a,␣b = 9.7 Hz.
2
3.1.2.26. Tetradecyl-β-d-galactopyranoside uronic
acid (26). 0.3 g (0.8 mmol) 20 were reacted using
General procedure 4. The product was purified by sil-
ica gel chromatography (ethyl acetate, then methanol).
Yield: 0.24 g (76%).
3J1,2 = 8.1, J3,4 = 3.6, J4,5 = 1.6, JCH -␤,␤
=
3
3
3
[α]2D0 = −22.1 (c = 0.2, methanol); C20H38O7
(390.2618); calc. C 61.51, H 9.81; found C 61.28, H
9.55.
3
3
3
3
6.6, JCH -␦,␦ = 6.6, JCH -␨,␨ = 6.1, JCH -␪,␪
=
3
3
3
3
6.6, Jalkyl-CH ,␫ = 6.6 Hz.
3
1H NMR (400 MHz, d4-MeOH): δ = 4.30 (d,
1H, H-1), 3.85 (dt, 1H, H-␣a), 3.78 (d, 1H, H-5),
3.48–3.57 (m, 2H, H-4, H-␣b), 3.37 (t, 1H, H-3),
3.22 (dd, 1H, H-2), 1.57–1.64 (m, 2H, ␤-CH2),
1.21–1.46 (m, 22H, –CH2–), 0.89 (t, 3H, alkyl-CH3);
3.1.2.29. Dodecyl-6-O-(4ꢀ-tolylsulfonyl)-␤-d-gluco-
pyranoside (29). 0.30 g (0.86 mmol) 2 were dis-
solved in 20 ml of chloroform, 55 mg tetra-n-butyla-
mmoniumbromide and 4 ml aqueous sodium hydrox-
ide (5%) were added. The mixture was cooled to
0 ◦C, and 0.21 (1.12 mmol) 4-toluenesulfonyl chlo-
ride were added in small portions. Afterwards the
mixture was stirred for 4 h at ambient tempera-
ture.
The phases were separated, the aqueous layer was
extracted with 20 ml of chloroform, the combined or-
ganic layers were washed with 20 ml of water. The or-
ganic phase was dried with MgSO4 and concentrated
in vacuo to obtain a viscous residue which was purified
by silica gel chromatography (chloroform–methanol
9:1). Yield: 0.33 g (77%).
3
3
3
3J1,2 = 8.1, J2,3 = 9.2, J3,4 = 3.6, J4,5
=
3
2
1.2, J␣a,␤-CH = 6.6, J␣a,␣b = 9.7 Hz.
2
3.1.2.27. (cis-9ꢀ-Octadecenyl)-␤-d-galactopyranoside
uronic acid (27). 0.52 g (1.2 mmol) 22 were reacted
using General procedure 4. The product was puri-
fied by silica gel chromatography (ethyl acetate, then
methanol). Yield: 0.5 g (93%).
[α]2D0 = −24 (c = 0.2, methanol); C24H44O7
(444.3087); calc. C 64.84, H 9.97; found C 65.15, H
8.83.
1H NMR (400 MHz, d4-MeOH): δ = 5.27–5.46
(m, 2H, H-olefinic), 4.23 (d, 1H, H-1), 3.93 (dt,
1H, H-␣a), 3.91 (d, 1H, H-5), 3.87 (dd, 1H, H-4),
3.43–3.70 (m, 3H, H-2, H-3, H-␣b), 1.96–2.13
(m, 4H, H-allylic), 1.59–1.69 (m, 2H, ␤-CH2),
1.27–1.45 (m, 30H, –CH2–), 0.94 (t, 3H, alkyl-CH3);
C25H42O8S (502.6648).
1H NMR (400 MHz, CDCl3+TMS): δ = 7.80–7.83
(m, 2H, ArH), 7.33–7.37 (m, 2H, ArH), 4.32 (d, 1H,
H-1), 4.21–4.29 (m, 2H, H-6a, H-6b), 3.93 (dt, 1H,
H-␣a), 3.59 (dt, 1H, H-␣b), 3.24–3.44 (m, 3H, H-3,
H-4, H-5), 3.35 (s, 3H, OCH3), 3.22 (dd, 1H, H-2),
1.65 (mc, 2H, ␤-CH2), 1.17–1.35 (m, 18H, –CH2–),
3
3
3
3J1,2 = 8.1, J3,4 = 3.6, J4,5 = 1.0, J␣a,␤-CH
=
2
2
6.6, J␣a,␣b = 9.7 Hz.
3
3
0.90 (t, 3H, alkyl-CH3); J1,2 = 8.1, J2,3
=
3
3
2
9.2, J␣a,␤-CH = 7.0, J␣b,␤-CH = 6.6, J␣a,␣b
=
2
2
3.1.2.28. [(2R,4R,6R,8R)-2,4,6,8-Tetramethyldecyl]-
β-d-galactopyranoside uronic acid (28). 0.3 g
(0.8 mmol) 24 were reacted using General procedure
4. The product was purified by silica gel chromatog-
raphy (ethyl acetate, then methanol). Yield: 0.12 g
(38%).
9.7 Hz.
3.1.2.30. Dodecyl-6-deoxy-6-azido-β-d-glucopyra-
noside (30). 0.3 g (0.6 mmol) 29 were dissolved
in 15 ml of dimethylsulfoxide. 121 mg (1.8 mmol)
sodium azide and 0.01 ml tetramethyl urea were

62
G. Milkereit et al. / Chemistry and Physics of Lipids 127 (2004) 47–63
added, and the mixture was stirred overnight at
50 ◦C.
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The solvent was removed in vacuo. The residue was
redissolved in 20 ml ethyl acetate and filtered. The or-
ganic phase was washed four times with 5 ml portions
of water, dried with MgSO4, and the solvent was re-
moved in vacuo. The product was purified by silica gel
chromatography (ethyl acetate–methanol 19:1). Yield:
354 mg (59%).
C18H35O5N3 (373.4905); calc. C 57.89, H 9.45;
found C 57.60, H 9.06.
1H NMR (400 MHz, d4-MeOH): δ = 4.27 (d, 1H,
H-1), 3.84–3.93 (m, 2H, H-6a, H-␣a), 3.66 (dd, 1H,
H-6b), 3.60 (dt, 1H, H-␣b), 3.26–3.34 (m, 3H, H-3,
H-4, H-5), 3.19 (dd, 1H, H-2), 1.68 (mc, 2H, ␤-CH2),
1.25–1.37 (m, 18H, –CH2–), 0.90 (t, 3H, alkyl-CH3);
3J1,2 = 8.1, J2,3 = 9.2, J5,6b = 5.6, J6a,b
=
3
3
3
3
3
2
12.1, J␣a,␤-CH = 7.0, J␣b,␤-CH = 6.6, J␣a,␣b
=
2
2
9.7 Hz.
3.1.2.31. Dodecyl-6-deoxy-6-amino-β-d-glucopyra-
noside (31). A mixture of 200 mg (0.5 mmol)
30 and 20 mg Pd/C (10%) in 10 ml of anhydrous
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complete.
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The catalyst was filtered off and the solvent was re-
moved in vacuo. The product was purified by column
chromatography (chloroform–methanol 9:1). Yield:
137 mg (79%).
[α]2D0 = −7.1 (c = 0.1, methanol); C18H37O5N
(347.4923); calc. C 62.22, H 10.73; found C 61.41, H
10.59.
1H NMR (400 MHz, d4-MeOH): δ = 4.24 (d,
1H, H-1), 3.96 (dt, 1H, H-␣a), 3.61 (dt, 1H, H-␣b),
3.20–3.47 (m, 4H, H-3, H-4, H-5, H-6a), 3.16 (dd,
1H, H-2), 3.09 (dd, 1H, H-6b), 1.65 (mc, 2H, ␤-CH2),
1.25–1.38 (m, 18H, –CH2–), 0.93 (t, 3H, alkyl-CH3);
3J1,2 = 8.1, J2,3 = 9.7, J5,6b = 5.1, J6a,b
=
3
3
3
3
3
2
12.2, J␣a,␤-CH = 7.0, J␣b,␤-CH = 6.6, J␣a,␣b
=
2
2
9.7 Hz.
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