Synthesis of selected aminodeoxy analogs of globotriosylceramide

Article abstract of DOI:10.1016/S0008-6215(99)00231-1

Four aminodeoxy analogs of globotriosylceramide (6''-, 4''-, 2''-, and 6'-aminodeoxy) were synthesized by glycosylation of 3-O-benzoylated azidosphingosine with the corresponding aminodeoxy-globotriose trichloroacetimidate, followed by reduction of the az

Full text of DOI:10.1016/S0008-6215(99)00231-1

www.elsevier.nl/locate/carres
Carbohydrate Research 322 (1999) 190–200
Synthesis of selected aminodeoxy analogs of
globotriosylceramide
Henrik C. Hansen, Go¨ran Magnusson *
Organic Chemistry 2, Center for Chemistry and Chemical Engineering, Lund Uni6ersity, PO Box 124,
SE-221 00 Lund, Sweden
Received 6 May 1999; accepted 13 August 1999
Abstract
Four aminodeoxy analogs of globotriosylceramide (6¦-, 4¦-, 2¦-, and 6%-aminodeoxy) were synthesized by
glycosylation of 3-O-benzoylated azidosphingosine with the corresponding aminodeoxy-globotriose trichloroacetimi-
date, followed by reduction of the azido group, N-acylation with 1-adamantaneacetic acid, and removal of the
protecting groups. © 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Globotriosylceramide aminodeoxy analogs
give salt bridges in the molecular complex. As
an attempt to increase the inhibitory power,
combination of the adamantylceramide agly-
con with aminodeoxy saccharides furnished
compounds 2–5 as a novel set of Gb3 analogs
(Fig. 1). We now report the synthesis of 2–5.
The exploitation of 2–5 as inhibitors of
globotriose-binding proteins will be reported
in due course.
1. Introduction
In the previous paper [1], we described the
synthesis of some aglycon analogs of
globotriosylceramide
[Gal-a-(1“4)Gal-b-
(1“4)Glc-b-(1“Cer), Gb3], including the
adamantylceramide analog 1 (Fig. 1). Com-
pound 1 was originally obtained [2] by hydrol-
ysis of the amide group of Gb3 followed by
N-acylation with 1-adamantaneacetic acid.
This semisynthetic compound was found to be
an efficient inhibitor of verotoxin binding [2].
We have also reported the synthesis of four
aminodeoxy analogs of Gb3 [3]. Computer
docking of Gb3 and verotoxin b subunit re-
vealed a close proximity between some hy-
droxyl groups of Gb3 to carboxyl groups in
the b subunit [4], indicating that exchange of
these hydroxyl groups for amino groups might
2. Results and discussion
Synthesis of compounds 2–5.—The known
[3] azido-functionalized 2-(trimethylsilyl)ethyl
(Me3SiEt) globotriosides 6a–d were each O-
debenzoylated with methanolic sodium
methoxide and the purified products were hy-
drogenated under slightly acidic conditions
(H2, Pd–C, EtOH, 0.1 M HCl) in order both
to remove the O-benzyl protecting groups and
reduce the azido groups to amino groups. The
crude amines were dissolved in methanol con-
taining a small amount of triethylamine, and
the slightly basic mixtures were treated with
* Corresponding author. Tel.: +46-46-222-8215; fax: +
46-46-222-8209.
E-mail address: goran.magnusson@orgk2.lth.se (G. Mag-
nusson)
0008-6215/99/$ - see front matter © 1999 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(99)00231-1

H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
191
Fig. 1. Inhibition of globotriose-binding proteins.
CF3COSEt [5] to yield the corresponding
crude N-trifluoroacetyl derivatives. Treatment
with acetic anhydride in pyridine and chro-
matography of the crude materials then fur-
nished 7a–d (Scheme 1) in 54–67% overall
yields over four reaction steps.
Compounds 7a–d were each treated with
CF3COOH in CH2Cl2 for 40 min, and chro-
matography of the crude materials yielded the
hemiacetals 8a–d (Scheme 1) in 81–95%
yields.
materials gave the N-adamantaneacetyl-Gb3
derivatives 11a–d (Scheme 2) in 75–87%
yields.
The N-trifluoroacetyl, O-acetyl and O-ben-
zoyl protecting groups of 11a–d were removed
by treatment with aqueous sodium hydroxide
in methanol, and the crude materials were
chromatographed on a reverse phase (C18)
column, using a waterꢀmethanol gradient,
which furnished the globotriosylceramide
analogs 2–5 (Scheme 2 and Fig. 1) in 73–84%
yields (purity\90%). Attempted chromatog-
raphy on silica gel was unsuccessful. The po-
larity profiles of 2–5 made it difficult to
Treatment of 8a–d with Cl3CCN in
dichloromethane [6] in the presence of diaz-
abicycloundecane (DBU), and chromatogra-
phy of the crude materials gave the
trichloroacetimidates 9a–d (Scheme 1) in 73–
83% yields. Compounds 9a–d were somewhat
labile under the acidic conditions of silica
1
obtain high-quality H NMR spectra, proba-
bly due to micelle formation.
chromatography. Consequently,
a
small
3. Experimental
amount of triethylamine was added to the
eluent, which permitted purification to a de-
gree of \90%.
Glycosylation of 3-O-benzoylated azidosph-
ingosine [7] was performed by treatment with
compounds 9a–d and BF3·OEt2 in dry
dichloromethane. Chromatography of the
crude materials gave the azidosphingosinyl
Gb3 derivatives 10a–d (Scheme 2) in 63–65%
yields.
The azido groups of 10a–d were reduced by
treatment with hydrogen sulfide in pyridine–
water mixture. The crude amines were dis-
solved in dichloromethane and acylated with
1-adamantaneacetic acid in the presence of N-
(3 - dimethylaminopropyl) - N% - ethylcarbodi-
imide (EDC). Chromatography of the crude
General experimental procedures and meth-
ods were as described previously [3]. The com-
pounds 1 [1] and 6a–d [3] have been reported.
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
hydroxy - octadec - 4 - enyl (h -
osyl)-(1“4)-(6-amino-6-deoxy-i-
pyranosyl)-(1“4)-i- -glucopyranoside (2).—
D
- galactopyran -
D
-galacto-
D
Compound 11a (5.5 mg, 0.004 mmol) was
dissolved in MeOH (5 mL), aq NaOH (1 M,
0.5 mL) was added, and the mixture was
stirred at room temperature (rt) for 18 h. The
reaction mixture was neutralized with Duolite
C436 (H+) resin, filtered, and concd. The
residue was chromatographed on a reverse-
phase column (Varian Mega Bond Elut C18
(water–MeOH 1:0“8:2“6:4“4:6“2:8“

192
H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
Scheme 1. (i) NaOMe, MeOH, 22 °C, 14–18 h; (ii) H2, Pd–C, EtOH, 0.1 M HCl, 22 °C, 14–18 h; (iii) CF3COSEt, MeOH, Et3N,
0 °C, 6 h; (iv) Ac2O, pyridine, 22 °C, 16 h; (v) CF3COOH, CH2Cl2, 22 °C, 40 min; (vi) Cl3CCN, CH2Cl2, DBU, 0 °C, 1 h.
D
- galactopyranosyl) - (1“4) - (i -
D
- galacto-
0:1, 6 mL of each) to give 2 (2.5 mg, 73%);
1
[h]2D2 +20° (c 0.1, MeOH); H NMR (3:1
pyranosyl)-(1“4)-i- -glucopyranoside (3).—
D
Compound 11b (10 mg, 0.007 mmol) was
treated essentially as described in the prepara-
tion of 2, thus yielding 3 (5.2 mg, 84%); [h]D22
+10° (c 0.3, MeOH); 1H NMR (3:1 CD3OD–
D2O): l (assignments of aglycon protons are
shown in italic) 5.65–5.77 (m, 1 H, H-5), 5.46
(dd, 1 H, J 7.8, 15.3 Hz, H-4), 3.10–4.47 (m),
0.80–2.20 (m, 46 H); HRMS Anal. Calcd for
C48H84O17N2Na [M+Na]: 983.5668. Found:
983.5692.
CD3OD–D2O): l (assignments of aglycon
protons are shown in italic) 5.69–5.78 (m, 1
H, H-5), 5.45 (br dd, 1 H, J 7.7, 15.4 Hz,
H-4), 4.46, 4.34 (br d, 1 H each, J 7.9 and 7.6
Hz, H-1,1%), 4.27 (br t, 1 H, J 6.2 Hz, H-5¦),
3.10–4.22 (m), 0.8–2.20 (m, 46 H); HRMS
Anal. Calcd for C48H84O17N2Na [M+Na]:
983.5668. Found: 983.5658.
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
hydroxy-octadec-4-enyl (2-amino-2-deoxy-h-

H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
193
Scheme 2. (i) (2S,3R,4E)-2-azido-3-(benzoyloxy)-4-octadecen-1-ol, BF3OEt2, CH2Cl2, 22 °C, 1.5 h; (ii) H2S, pyridine, H2O, 0 °C,
1 h“22 °C, 44 h; (iii) adamantaneacetic acid, EDC, CH2Cl2, 22 °C, 16 h; (iv) NaOH, H2O, MeOH, 22 °C, 18 h.
l (assignments of aglycon protons are shown
in italic) 7.90 (m, 1 H, NHCO), 5.66–5.78 (m,
1 H, H-5), 5.45 (br dd, 1 H, J 7.6, 15.1 Hz,
H-4), 4.44, 4.34 (br d, 1 H each, J 7.6 and 7.8
Hz, H-1,1%), 3.20–4.35 (m), 2.73–2.89 (m, 2
H), 0.80–2.20 (m, 46 H); HRMS Anal. Calcd
for C48H84O17N2Na [M+Na]: 983.5668.
Found: 983.5686.
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
hydroxy - octadec - 4 - enyl (4 - amino - 4 - deoxy-
h-
D
-galactopyranosyl)-(1“4)-(i-
D
-galacto-
-glucopyranoside (4).—
pyranosyl)-(1“4)-i-
D
Compound 11c (11 mg, 0.007 mmol) was
treated essentially as described in the prepara-
tion of 2, thus yielding 4 (5.4 mg, 78%); [h]D22
+17° (c 0.5, MeOH); 1H NMR (3:1 CD3OD–
D2O): l (assignments of aglycon protons are
shown in italic) 5.63–5.76 (m, 1 H, H-5),
5.42–5.51 (m, 1 H, H-4), 4.31 (br d, 1 H, J 7.9
Hz, H-1% or H-1), 3.10–4.45 (m), 0.80–2.20
(m, 46 H); HRMS Anal. Calcd for
C48H84O17N2Na [M+Na]: 983.5668. Found:
983.5652.
2-(Trimethylsilyl)ethyl
acetyl-h- -galactopyranosyl)-(1“4)-(2,3-di-
O-acetyl-6-deoxy-6-trifluoroacetamido-i-
galactopyranosyl)-(1“4)-2,3,6-tri-O-acetyl-
i- -glucopyranoside (7a).—Compound 6a [3]
(2,3,4,6-tetra-O-
D
D
-
D
(200 mg, 0.132 mmol) was treated with 0.5 M
methanolic NaOMe for 18 h and the reaction
mixture was neutralized with Duolite C436
(H+) resin, filtered, and concentrated. The
residue was chromatographed (SiO2, 20:10:3
toluene–EtOAc–MeOH) and the product was
dissolved in a mixture of EtOH (10 mL) and
0.1 M aqueous HCl (1.1 mL) and hydro-
genated (Pd–C, H2, 1 atm) for 14 h. The
reaction mixture was filtered through Celite
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
hydroxy-octadec-4-enyl (6-amino-6-deoxy-h-
galactopyranosyl) - (1“4) - (i - - galactopyr-
anosyl)-(1“4)-i- -glucopyranoside (5).—
D
-
D
D
Compound 11d (18 mg, 0.012 mmol) was
treated essentially as described in the prepara-
tion of 2, which gave 5 (8 mg, 73%); [h]2D2 +4°
1
(c 0.5, MeOH); H NMR (3:1 CD3OD–D2O):

194
H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
4.83–4.90 (m, 2 H, H-3%,2), 4.57 (d, 1 H, J 7.5
Hz, H-1’), 4.55–4.62 (m, 2 H, incl. H-2¦), 4.52
(br t, 1 H, J 6.5 Hz, H-5¦), 4.47 (d, 1 H, J 8.0
Hz, H-1), 4.43 (dd, 1 H, J 6.0, 11.2 Hz),
4.04–4.17 (m, 3 H), 4.05 (d, 1 H, J 2.0 Hz,
H-4%), 3.87–3.98 (m, 2 H), 3.76–3.83 (m, 2 H,
incl. H-4), 3.64–3.70 (m, 1 H), 3.57 (dt, 1 H,
J 6.5, 9.8 Hz, OCH2CH2Si), 2.16, 2.08, 2.07,
2.055, 2.050, 2.04, 2.025, 2.00 (8 s, 27 H,
OAc), 0.84–1.01 (m, 2 H, CH2Si), 0.00 (s, 9
and concentrated. The residue was dissolved
in MeOH (10 mL) and Et3N (0.05 mL),
cooled to 0 °C, and CF3COSEt (0.06 mL, 0.47
mmol) was added. The mixture was stirred
under N2 while slowly allowed to attain rt.
After 6 h, toluene (5 mL) was added and the
mixture was concd. The residue was treated
with a 1:1 mixture of Ac2O and pyridine (10
mL) for 16 h and the mixture was co-concd
with toluene. The residue was chro-
matographed (1:1 EtOAc–heptane) to give 7a
13
H, SiMe3); C NMR (CDCl3): d 171.4, 171.2,
1
(77 mg, 54%); [h]2D2 +59° (c 1.0, CHCl3); H
170.74, 170.69, 170.6, 170.5, 170.4, 170.0,
169.5, 158.1 (q), 116.0 (q), 100.5, 100.2, 99.2,
75.3, 73.0, 72.9, 72.6, 72.1, 69.7, 67.9, 67.7,
67.6, 67.2, 63.2, 60.8, 60.6, 50.1, 21.27, 21.25,
21.17, 21.16, 21.10, 20.98, 20.97, 20.93, 18.3,
−1.0; HRMS calcd for C43H62O25F3NSiNa
[M+Na]: 1100.3230, found 1100.3250.
NMR (CDCl3): l 7.64 (br d, 1 H, J 5.4 Hz,
NH), 5.54 (br d, 1 H, J 3.2 Hz, H-4¦), 5.34
(dd, 1 H, J 3.3, 11.0 Hz, H-3¦), 5.23 (dd, 1 H,
J 3.4, 11.0 Hz, H-2¦), 5.16 (br t, 1 H, J 8.2 Hz,
H-3), 5.10 (dd, 1 H, J 7.5, 10.5 Hz, H-2%), 4.97
(d, 1 H, J 3.4 Hz, H-1¦), 4.94 (dd, 1 H, J 7.1,
8.2 Hz, H-2), 4.74 (dd, 1 H, J 2.6, 10.5 Hz,
H-3%), 4.60 (d, 1 H, J 7.4 Hz, H-1%), 4.53 (d, 1
H, J 6.9 Hz, H-1), 4.49–4.55 (m, 1 H, H-6),
4.47 (br t, 1 H, J 7.1 Hz, H-5¦), 4.18 (dd, 1 H,
J 8.2, 10.8 Hz, H-6¦), 4.04–4.14 (m, 3 H,
H-4%,6¦,6), 3.88–4.00 (m, 2 H, H-4 and
OCH2CH2Si), 3.84 (ddd, 1 H, J 2.0, 8.7, 14.0
Hz, H-6%), 3.65–3.77 (m, 2 H, H-5,5%), 3.47–
3.62 (m, 2 H, H-6% and OCH2CH2Si), 2.14,
2.10, 2.09, 2.07, 2.06, 2.05, 1.98 (7 s, 27 H,
OAc), 0.84–1.03 (m, 2 H, CH2Si), 0.01 (s, 9
H, SiMe3); 13C NMR (CDCl3): l 171.12,
171.10, 171.0, 170.9, 170.6, 170.5, 170.4, 170.2,
169.4, 158.3 (q), 116.2 (q), 100.6, 100.5, 100.2,
78.4, 76.1, 73.8, 72.8, 72.7, 72.1, 69.14, 69.12,
68.3, 68.0, 67.5, 63.2, 61.0, 41.2, 21.4, 21.3,
21.25, 21.20, 21.19, 21.12, 21.06, 21.04, 20.97,
18.3, −1.0; HRMS Anal. Calcd for
C43H62O25F3NSiNa [M+Na]: 1100.3230.
Found: 1100.3198.
2-(Trimethylsilyl)ethyl (2,3,6-tri-O-acetyl-4-
deoxy-4-trifluoroacetamido-h-
osyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
pyranosyl) - (1“4) - 2,3,6 - tri - O - acetyl - i -
D
-galactopyran-
D
-galacto-
D
-
glucopyranoside (7c).—Compound 6c [3] (165
mg, 0.11 mmol) was treated essentially as
described in the preparation of 7a, thus yield-
ing 7c (112 mg, 67%); [h]2D1 +29° (c 1.0,
1
CHCl3); H NMR (CDCl3): l 6.75 (d, 1 H, J
9.2 Hz, NH), 5.38 (dd, 1 H, J 4.2, 11.1 Hz,
H-3¦), 5.20 (t, 1 H, J 9.1 Hz, H-3), 5.08 (dd, 1
H, J 7.7, 10.9 Hz, H-2%), 5.00 (d, 1 H, J 3.8
Hz, H-1¦), 4.93 (dd, 1 H, J 3.8, 11.1 Hz,
H-2¦), 4.88 (dd, 1 H, J 8.0, 9.4 Hz, H-2),
4.82–4.89 (m, 1 H, H-4¦), 4.69 (dd, 1 H, J 2.5,
10.9 Hz, H-3%), 4.60–4.65 (m, 1 H, H-5¦), 4.53
(d, 1 H, J 7.7 Hz, H-1%), 4.50 (d, 1 H, J 7.9
Hz, H-1), 4.46 (dd, 1 H, J 2.0, 11.4 Hz, H-6),
4.42 (dd, 1 H, J 6.4, 11.0 Hz, H-6%), 4.24 (dd,
1 H, J 7.3, 11.6 Hz, H-6¦), 4.18 (dd, 1 H, J
4.3, 11.7 Hz, H-6¦), 4.15 (dd, 1 H, J 6.9, 11.0
Hz, H-6%), 4.11 (dd, 1 H, J 5.5, 11.8 Hz, H-6),
4.06 (br d, 1 H, J 2.3 Hz, H-4%), 3.95 (dt, 1 H,
J 5.7, 9.8 Hz, OCH2CH2Si), 3.75–3.83 (m, 2
H, H-4,5%), 3.64 (ddd, 1 H, J 1.9, 5.4, 9.7 Hz,
H-5), 3.57 (dt, 1 H, J 6.8, 9.8 Hz,
OCH2CH2Si), 2.11, 2.090, 2.086, 2.075, 2.062,
2.059, 2.036, 2.00 (8 s, 27 H, OAc), 0.84–1.01
(m, 2 H, CH2Si), 0.00 (s, 9 H, SiMe3); 13C
NMR (CDCl3): l 171.2, 171.1, 170.92, 170.90,
170.6, 170.14, 170.11, 169.4, 158.2 (q), 116.1
(q), 101.4, 100.3, 99.9, 78.1, 77.0, 73.8, 73.4,
72.8, 72.3, 72.1, 69.2, 69.15, 67.9, 67.7, 66.4,
2-(Trimethylsilyl)ethyl (3,4,6-tri-O-acetyl-2-
deoxy-2-trifluoroacetamido-h-
osyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
pyranosyl) - (1“4) - 2,3,6 - tri - O - acetyl - i -
D
-galactopyran-
D
-galacto-
D
-
glucopyranoside (7b).—Compound 6b [3] (220
mg, 0.144 mmol) was treated essentially as
described in the preparation of 7a, thus yield-
ing 7b (97 mg, 63%); [h]2D2 +28° (c 1.0,
1
CHCl3); H NMR (CDCl3): l 7.55 (d, 1 H, J
8.5 Hz, NH), 5.56 (br d, 1 H, J 2.9 Hz, H-4¦),
5.36 (dd, 1 H, J 3.1, 11.6 Hz, H-3¦), 5.23 (t, 1
H, J 9.2 Hz, H-3), 5.13 (dd, 1 H, J 7.5, 10.9
Hz, H-2%), 5.06 (d, 1 H, J 3.5 Hz, H-1¦),

H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
195
(3,4,6-Tri-O-acetyl-2-deoxy-2-trifluoroacet-
amido-h- -galactopyranosyl)-(1“4)-(2,3,6-
tri-O-acetyl-i- -galactopyranosyl)-(1“4)-
2,3,6-tri-O-acetyl-i- -glucopyranose (8b).—
Compound 7b (55 mg, 0.051 mmol) was
treated essentially as described in the prepara-
tion of 8a, thus yielding 8b (47.1 mg, 94%);
HRMS Anal. Calcd for C38H50O25F3NNa
[M+Na]: 1000.2522. Found: 1000.2526.
(2,3,6-Tri-O-acetyl-4-deoxy-4-trifluoroac-
62.8, 61.8, 61.7, 50.5, 21.4, 21.3, 21.22, 21.15,
21.12, 21.07, 21.0, 20.9, 18.3, −1.0; HRMS
Anal. Calcd for C43H62O25F3NSiNa [M+Na]:
1100.3230. Found: 1100.3247.
D
D
D
2-(Trimethylsilyl)ethyl (2,3,4-tri-O-acetyl-6-
deoxy-6-trifluoroacetamido-h-
osyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
pyranosyl) - (1“4) - 2,3,6 - tri - O - acetyl - i -
D
-galactopyran-
D
-galacto-
D
-
glucopyranoside (7d).—Compound 6d [3] (51
mg, 0.033 mmol) was treated essentially as
described in the preparation of 7a, thus yield-
ing 7d (22.5 mg, 63%); [h]2D2 +49° (c 0.5,
etamido - h -
(2,3,6 - tri - O - acetyl - i -
(1“4)-2,3,6-tri-O-acetyl-i-
D
- galactopyranosyl) - (1“4) -
- galactopyranosyl) -
-glucopyranose
D
1
CHCl3); H NMR (CDCl3): l 7.40–7.48 (m, 1
D
H, NH), 5.45 (bd, 1 H, J 3.4 Hz, H-4¦), 5.39
(dd, 1 H, J 3.4, 10.9 Hz, H-3¦), 5.20 (t, 1 H, J
9.2 Hz, H-3), 5.15 (dd, 1 H, J 3.5, 10.9 Hz,
H-2¦), 5.12 (dd, 1 H, J 7.7, 11.1 Hz, H-2%),
5.02 (d, 1 H, J 3.5 Hz, H-1¦), 4.91 (dd, 1 H, J
8.0, 9.5 Hz, H-2), 4.72 (dd, 1 H, J 2.2, 11.1
Hz, H-3%), 4.54 (d, 1 H, J 7.7 Hz, H-1%), 4.50
(d, 1 H, J 7.9 Hz, H-1), 4.39–4.51 (m, 3 H,
H-5¦,6%,6), 4.18 (dd, 1 H, J 6.8, 11.1 Hz, H-6%),
4.14 (dd, 1 H, J 5.4, 11.8 Hz, H-6), 4.03 (br d,
1 H, J 2.1 Hz, H-4%), 3.97 (dt, 1 H, J 5.7, 10.2
Hz, OCH2CH2Si), 3.76–3.86 (m, 3 H, H-
4,5%,6¦), 3.66 (ddd, 1 H, J 1.9, 5.3, 9.8 Hz,
H-5), 3.58 (dt, 1 H, J 6.7, 9.9 Hz,
OCH2CH2Si), 3.39 (br dt, 1 H, J 5.3, 13.5 Hz,
H-6¦), 2.20, 2.13, 2.11, 2.10, 2.095, 2.075, 2.06,
2.045, 1.99 (9 s, 27 H, OAc), 0.83–1.02 (m, 2
H, CH2Si), 0.02 (s, 9 H, SiMe3); 13C NMR
(CDCl3): l 171.00, 170.97, 170.94, 170.8,
170.6, 170.4, 170.13, 170.10, 100.97, 100.5,
99.8, 77.6, 76.8, 73.6, 73.4, 73.0, 72.3, 72.1,
69.6, 69.4, 68.1, 68.0, 67.4, 62.7, 62.1, 39.0,
21.4, 21.3, 21.21, 21.19, 21.1, 18.3, −1.0;
HRMS Anal. Calcd for C43H62O25F3NSiNa
[M+Na]: 1100.3230. Found: 1100.3210.
(8c).—Compound 7c (90 mg, 0.083) was
treated essentially as described in the prepara-
tion of 8a, thus yielding 8c (66 mg, 81%);
HRMS Anal. Calcd for C38H50O25F3NNa
[M+Na]: 1000.2522. Found: 1000.2508.
(2,3,4-Tri-O-acetyl-6-deoxy-6-trifluoroacet-
amido-h-
tri-O-acetyl-i-
2,3,6-tri-O-acetyl-i-
D
-galactopyranosyl)-(1“4)-(2,3,6-
-galactopyranosyl)-(1“4)-
-glucopyranose (8d).—
D
D
Compound 7d (54 mg, 0.05 mmol) was treated
essentially as described in the preparation of
8a, thus yielding 8d (45.8 mg, 93%); HRMS
Anal. Calcd for C38H50O25F3NNa [M+Na]:
1000.2522. Found: 1000.2504.
(2,3,4,6-Tetra-O-acetyl-h-
osyl)-(1“4)-(2,3-di-O-acetyl-6-deoxy-6-tri-
fluoroacetamido-i- -galactopyranosyl)-(1“4)
-2,3,6-tri-O-acetyl-h- -glucopyranosyl tri-
D
-galactopyran-
D
D
chloroacetimidate (9a).—Compound 8a (64
mg, 0.065 mmol) was dissolved in a mixture of
CH2Cl2 (3 mL) and Cl3CCN (0.20 mL, 2
mmol) and cooled to 0 °C under N2. Diazabi-
cycloundecane (DBU, 0.020 mL, 0.13 mmol)
was added and after 1 h the reaction mixture
was concd. The residue was chromatographed
(1:1 EtOAc–heptane, 3% Et3N) to give 9a (61
(2,3,4,6-Tetra-O-acetyl-h-
osyl)-(1“4)-(2,3-di-O-acetyl-6-deoxy-6-tri-
fluoroacetamido-i- -galactopyranosyl)-(1“4)
-2,3,6-tri-O-acetyl-i- -glucopyranose (8a).—
D
-galactopyran-
1
mg, 83%; purity: ꢀ90%). H NMR (CDCl3):
D
l 8.66 (s, 1 H, ꢁNH), 7.64 (br d, 1 H, J 5.7
Hz, NHCO), 6.49 (d, 1 H, J 4.1 Hz, H-1), 5.54
(br d, 1 H, J 3.1 Hz, H-4¦), 5.44 (br t, 1 H, J
8.0 Hz, H-3), 5.35 (dd, 1 H, J 3.3, 11.0 Hz,
H-3¦), 5.29 (dd, 1 H, J 4.2, 8.4 Hz, H-2), 5.24
(dd, 1 H, J 3.4, 11.0 Hz, H-2¦), 5.13 (dd, 1 H,
J 7.5, 10.5 Hz, H-2%), 4.98 (d, 1 H, J 3.3 Hz,
H-1¦), 4.77 (dd, 1 H, J 2.7, 10.4 Hz, H-3%),
4.64 (d, 1 H, J 7.5 Hz, H-1%), 4.40–4.51 (m, 2
H, incl. H-5¦), 4.05–4.24 (m, 5 H, incl. H-
4%,5), 3.92–4.01 (m, 1 H, H-4), 3.72–3.89 (m,
D
Compound 7a (47 mg, 0.044 mmol) was dis-
solved in a mixture of CH2Cl2 (1 mL) and
trifluoroacetic acid (2 mL) and stirred at rt for
40 min, then co-concd with n-propyl acetate
(5 mL) and toluene (2×5 mL) [8]. The residue
was chromatographed (3:1 EtOAc–heptane)
to give 8a (40.3 mg, 95%); HRMS Anal. Calcd
for C38H50O25F3NNa [M+Na]: 1000.2522.
Found: 1000.2504.

196
H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
H-2¦), 4.86 (br dd, 1 H, J 3.7, 9.2 Hz, H-4¦),
4.73 (dd, 1 H, J 2.3, 10.8 Hz, H-3%), 4.62–4.67
(m, 1 H), 4.57 (d, 1 H, J 7.8 Hz, H-1%),
4.45–4.52 (m, 2 H), 4.11–4.31 (m, 6 H, incl.
H-5), 4.04 (br d, 1 H, J 2.2 Hz, H-4%), 3.89 (t,
1 H, J 9.2 Hz, H-4), 3.80 (t, 1 H, J 6.9 Hz),
2.12, 2.110, 2.105, 2.100, 2.08, 2.065, 2.055,
2.025, 2.02 (9 s, 27 H, OAc); 13C NMR
(CDCl3): l 171.0, 170.9, 170.8, 170.6, 170.1,
169.4, 161.4, 158.3 (q), 116.1 (q), 101.5, 99.9,
93.3, 78.1, 76.5, 73.4, 72.1, 71.3, 70.33, 70.26,
69.3, 67.7, 66.4, 62.1, 61.7, 61.6, 50.6, 21.4,
21.3, 21.21, 21.15, 21.1, 21.0; HRMS Anal.
Calcd for C40H50O25N2Cl3F3Na [M+Na]:
1143.1618. Found: 1143.1611.
2 H), 3.47–3.61 (m, 1 H), 2.15, 2.13, 2.115,
2.10, 2.09, 2.075, 2.070, 2.06, 1.99 (9 s, 27 H,
OAc); 13C NMR (CDCl3): l 171.1, 171.0,
170.9, 170.8, 170.54, 170.48, 170.2, 169.5,
161.1, 158.2 (q), 116.2 (q), 101.4, 100.2, 93.3,
78.4, 76.0, 73.6, 72.9, 71.4, 69.2, 69.1, 68.9,
68.3, 68.0, 67.4, 62.4, 60.9, 41.0, 21.33, 21.26,
21.2, 21.13, 21.07, 21.03, 21.00; HRMS Anal.
Calcd for C40H50O25N2Cl3F3Na [M+Na]:
1143.1618. Found: 1143.1611.
(3,4,6-Tri-O-acetyl-2-deoxy-2-trifluoroacet-
amido-h-
tri-O-acetyl-i-
2,3,6 - tri - O - acetyl - h -
D
-galactopyranosyl)-(1“4)-(2,3,6-
-galactopyranosyl)-(1“4)-
- glucopyranosyl tri -
D
D
chloroacetimidate (9b).—Compound 8b (45
mg, 0.046 mmol) was treated essentially as
described in the preparation of 9a, thus yield-
ing 9b (37 mg, 73%); [h]2D2 +62° (c 1.0,
(2,3,4-Tri-O-acetyl-6-deoxy-6-trifluoroacet-
amido-h-
tri-O-acetyl-i-
2,3,6 - tri - O - acetyl - h -
D
-galactopyranosyl)-(1“4)-(2,3,6-
-galactopyranosyl)-(1“4)-
- glucopyranosyl tri -
D
1
CHCl3); H NMR (CDCl3): l 8.67 (s, 1 H,
D
ꢁNH), 7.43 (d, 1 H, J 8.4 Hz, NHCO), 6.49
(d, 1 H, J 3.8 Hz, H-1), 5.54–5.62 (m, 2 H,
H-4¦,3), 5.36 (dd, 1 H, J 3.1, 11.6 Hz, H-3¦),
5.15 (dd, 1 H, J 7.5, 10.7 Hz, H-2%), 5.09 (d, 1
H, J 3.9 Hz, H-1¦), 5.06 (dd, 1 H, J 3.8, 9.9
Hz, H-2), 4.87 (dd, 1 H, J 2.5, 10.8 Hz, H-3%),
4.63 (d, 1 H, J 7.6 Hz, H-1%), 4.44–4.65 (m, 4
H, incl. H-2¦), 4.05–4.24 (m, 4 H), 4.05 (d, 1
H, J 2.2 Hz, H-4%), 3.80–3.96 (m, 3 H, incl.
H-4), 2.17, 2.09, 2.085, 2.080, 2.06, 2.05, 2.015
chloroacetimidate (9d).—Compound 8d (45
mg, 0.046 mmol) was treated essentially as
described in the preparation of 9a, thus yield-
1
ing 9d (42.9 mg, 83%; purity: \90%). H
NMR (CDCl3): l 8.67 (s, 1 H, ꢁNH), 7.35–
7.44 (m, 1 H, NHCO), 6.50 (d, 1 H, J 3.8 Hz,
H-1), 5.55 (t, 1 H, J 9.7 Hz, H-3), 5.45 (br d,
1 H, J 3.2 Hz, H-4¦), 5.39 (dd, 1 H, J 3.4, 10.9
Hz, H-3¦), 5.10–5.18 (m, 2 H, H-2%,2¦), 5.08
(dd, 1 H, J 3.8, 10.2 Hz, H-2), 5.03 (d, 1 H, J
3.5 Hz, H-1¦), 4.71 (dd, 1 H, J 2.0, 11.1 Hz,
H-3%), 4.56 (d, 1 H, J 7.7 Hz, H-1%), 4.37–4.53
(m, 3 H, incl. H-5¦), 4.10–4.24 (m, 3 H), 4.04
(br d, 1 H, J 1.9 Hz, H-4%), 3.76–3.91 (m, 3 H,
incl. H-4,6¦), 2.19, 2.12, 2.105, 2.100, 2.07,
2.06, 2.02, 1.99 (8 s, 27 H, OAc); 13C NMR
(CDCl3): l 171.0, 170.9, 170.8, 170.6, 170.1,
170.0, 161.4, 158.0 (q), 116.0 (q), 101.2, 99.8,
93.3, 77.6, 76.3, 73.6, 72.4, 71.4, 70.2, 70.0,
69.5, 69.4, 68.2, 68.1, 67.4, 62.04, 61.99, 39.1,
21.4, 21.3, 21.2, 21.11, 21.06, 20.9; HRMS
Anal. Calcd for C40H50O25N2Cl3F3Na [M+
Na]: 1143.1618. Found: 1143.1621.
13
(7 s, 27 H, OAc); C NMR (CDCl3): l 171.4,
171.2, 170.8, 170.7, 170.6, 170.5, 170.4, 169.9,
169.4, 161.4, 100.8, 99.3, 93.3, 76.6, 75.3, 72.8,
71.9, 71.4, 70.7, 69.8, 69.6, 67.8, 67.7, 67.2,
62.6, 60.7, 60.4, 50.4, 21.31, 21.27, 21.22,
21.11, 21.00, 20.98, 20.95, 20.9; HRMS Anal.
Calcd for C40H50O25N2Cl3F3Na [M+Na]:
1143.1618. Found: 1143.1606.
(2,3,6-Tri-O-acetyl-4-deoxy-4-trifluoroacet-
amido-h-
tri-O-acetyl-i-
2,3,6 - tri - O - acetyl - h -
D
-galactopyranosyl)-(1“4)-(2,3,6-
-galactopyranosyl)-(1“4)-
- glucopyranosyl tri -
D
D
chloroacetimidate (9c).—Compound 8c (65
mg, 0.066 mmol) was treated essentially as
described in the preparation of 9a, thus yield-
ing 9c (61 mg, 83%); [h]2D2 +197° (c 0.1,
(2S,3R,4E)-2-Azido-3-benzoyloxyoctadec-
4-enyl (2,3,4,6-tetra-O-acetyl-h- -galactopyr-
D
anosyl)-(1“4)-(2,3-di-O-acetyl-6-deoxy-6-
trifluoroacetamido - i - - galactopyranosyl) -
(1“4)-2,3,6-tri-O-acetyl-i- -glucopyranoside
1
CHCl3); H NMR (CDCl3): l 8.07 (s, 1 H,
D
ꢁNH), 6.60 (br d, 1 H, J 9.0 Hz, NHCO), 6.50
(d, 1 H, J 3.7 Hz, H-1), 5.58 (t, 1 H, J 9.6 Hz,
H-3), 5.41 (dd, 1 H, J 4.1, 11.2 Hz, H-3¦),
5.07–5.14 (m, 2 H, H-2%,2), 5.05 (d, 1 H, J 3.8
Hz, H-1¦), 4.93 (dd, 1 H, J 3.7, 11.2 Hz,
D
(10a).—Compound 9a (6.5 mg, 0.006 mmol)
and (2S,3R,4E)-2-azido-3-(benzoyloxy)-4-oc-
tadecen-1-ol [7] (5 mg, 0.012 mmol) were dis-
solved in dry CH2Cl2 (3 mL). Molecular sieves

H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
197
14.9 Hz, H-5), 5.51–5.64 (m, 3 H, H-4¦,4,3),
5.36 (dd, 1 H, J 3.1, 11.6 Hz, H-3¦), 5.24 (t, 1
H, J 9.0 Hz, H-3), 5.14 (dd, 1 H, J 7.5, 10.8
Hz, H-2%), 5.07 (d, 1 H, J 3.5 Hz, H-1¦), 4.93
(br t, 1 H, J 8.5 Hz, H-2), 4.87 (dd, 1 H, J 2.5,
10.8 Hz, H-3%), 4.49–4.63 (m, 5 H, incl. H-
1,1%,2¦,5¦), 4.44 (dd, 1 H, J 5.9, 11.1 Hz),
4.01–4.19 (m, 4 H, incl. H-4%), 3.77–3.97 (m, 5
H, incl. H-4), 3.66–3.73 (m, 1 H), 3.60 (dd, 1
H, J 5.7, 10.3 Hz), 2.17, 2.085, 2.080, 2.06,
2.045, 2.03, 2.015 (7 s, 27 H, OAc), 1.21–1.43
(m, 24 H,CH2), 0.89 (t, 3 H, J 6.8 Hz, CH3);
13C NMR (CDCl3): l 171.3, 171.2, 170.74,
170.69, 170.65, 170.47, 170.4, 170.0, 169.5,
165.5, 139.5, 133.7, 130.3, 130.2, 128.9, 123.1,
100.6, 100.5, 99.2, 77.0, 75.3, 75.1, 73.2, 72.9,
72.7, 72.3, 72.1, 69.6, 68.7, 67.8, 67.7, 67.2,
63.9, 63.0, 60.7, 60.6, 50.2, 32.8, 32.4, 30.1,
30.0, 29.83, 29.79, 29.6, 29.1, 23.1, 21.3, 21.2,
21.1, 21.0, 14.6; HRMS Anal. Calcd for
AW-300 (100 mg) were added, the mixture
was stirred for 20 min, and BF3·OEt2 (0.0012
mL, 0.01 mmol) was added. The reaction mix-
ture was stirred at rt for 1.5 h, filtered through
Celite, washed with a saturated aqueous
NaHCO3, dried, and concd. The residue was
chromatographed (1:1 EtOAc–heptane) to
give 10a (5 mg, 63%); [h]2D2 +44° (c 0.7,
1
CHCl3); H NMR (CDCl3): l (assignments of
aglycon protons are shown in italic) 8.04–8.08
(m, 2 H, Ar–H), 7.56–7.63 (m, 2 H, NH and
Ar–H), 7.44–7.50 (m, 2 H, Ar–H), 5.94 (dt, 1
H, J 6.8, 15.0 Hz, H-5), 5.63 (dd, 1 H, J 4.1,
8.1 Hz, H-3), 5.51–5.60 (m, 3 H, incl. H-4¦,
H-4), 5.35 (dd, 1 H, J 3.3, 11.1 Hz, H-3¦), 5.24
(dd, 1 H, J 3.4, 11.1 Hz, H-2¦), 5.21 (t, 1 H, J
7.6 Hz, H-3), 5.11 (dd, 1 H, J 7.5, 10. 5 Hz,
H-2%), 4.95–5.01 (m, 2 H, H-1¦, H-2), 4.75
(dd, 1 H, J 2.7, 10.5 Hz, H-3%), 4.61 (2 d, 1 H
each, J 6.2, 7.5 Hz, H-1,1%), 4.43–4.52 (m, 2
H, incl. H-5¦), 4.19 (dd, 1 H, J 8.2, 10.8 Hz),
4.07–4.14 (m, 2 H, incl. H-4), 4.04 (dd, 1 H, J
5.8, 12.0 Hz), 3.87–4.00 (m, 3 H, H-1, H-2,
H-4), 3.84 (dq, 1 H, J 2.2, 14.1 Hz), 3.67–3.77
(m, 2 H), 3.62 (dd, 1 H, J 3.4, 10.1 Hz, H-1),
3.48–3.58 (m, 1 H), 2.15, 2.13, 2.12, 2.10,
2.07, 2.065, 2.055, 2.03, 1.995 (9 s, 27 H,
OAc), 1.20–1.45 (m, 24 H,CH2), 0.89 (t, 3 H,
J 6.9 Hz, CH3); 13C NMR (CDCl3): l 171.2,
171.0, 170.9, 170.6, 170.4, 170.3, 169.4, 165.5,
139.4, 133.7, 130.3, 130.2, 128.9, 123.1, 101.0,
100.9, 100.2, 78.5, 75.9, 75.0, 73.8, 73.3, 72.8,
72.7, 71.8, 69.2, 69.1, 68.9, 68.3, 68.0, 67.5,
63.9, 62.9, 60.9, 41.3, 32.8, 32.4, 30.1, 30.0,
29.83, 29.79, 29.6, 29.1, 23.1, 21.3, 21.2, 21.12,
21.08, 21.05, 20.96, 14.6; HRMS Anal. Calcd
for C63H87O27F3N4Na [M+Na]: 1411.5407.
Found: 1411.5432.
C63H87O27F3N4Na
Found: 1411.5449.
(2S,3R,4E)-2-Azido-3-benzoyloxyoctadec-
4-enyl (2,3,6-tri-O-acetyl-4-deoxy-4-trifluoro-
[M+Na]:
1411.5407.
acetamido - h -
(2,3,6 - tri - O - acetyl - i -
(1“4)-2,3,6-tri-O-acetyl-i-
D
- galactopyranosyl) - (1“4) -
- galactopyranosyl) -
-glucopyranoside
D
D
(10c).—Compound 9c (17 mg, 0.015 mmol)
was treated essentially as described in the
preparation of 10a, thus yielding 10c (13.5 mg,
1
64%); [h]2D2 +14° (c 1.0, CHCl3); H NMR
(CDCl3): l (assignments of aglycon protons
are shown in italic) 8.03–8.08 (m, 2 H, Ar–
H), 7.55–7.62 (m, 1 H, Ar–H), 7.43–7.50 (m,
2 H, Ar–H), 6.65 (d, 1 H, J 9.2 Hz, NH), 5.93
(dt, 1 H, J 6.8, 15.0 Hz, H-5), 5.51–5.64 (m, 2
H, H-3,4), 5.39 (dd, 1 H, J 4.1, 11.1 Hz,
H-3¦), 5.21 (t, 1 H, J 8.9 Hz, H-3), 5.09 (dd, 1
H, J 7.8, 10.9 Hz, H-2%), 5.02 (d, 1 H, J 3.8
Hz, H-1¦), 4.90–4.97 (m, 2 H, H-2,2¦), 4.85
(br dd, 1 H, J 2.9, 9.0 Hz, H-4¦), 4.71 (dd, 1
H, J 2.4, 10.9 Hz, H-3%), 4.60–4.66 (m, 1 H,
H-5¦), 4.55 (d, 2 H, J 7.7 Hz, H-1,1%), 4.40–
4.50 (m, 2 H), 4.01–4.29 (m, 5 H, incl. H-
4%,6¦), 3.75–3.97 (m, 4 H, incl. H-2), 3.66
(ddd, 1 H, J 2.0, 5.4, 9.8 Hz), 3.59 (dd, 1 H, J
5.8, 10.3 Hz), 2.015, 2.045, 2.055, 2.07, 2.09,
2.10 (6 s, 27 H, OAc), 1.20–1.45 (m, 24 H,
(2S,3R,4E)-2-Azido-3-benzoyloxyoctadec-
4-enyl (3,4,6-tri-O-acetyl-2-deoxy-2-trifluoro-
acetamido - h -
(2,3,6 - tri - O - acetyl - i -
(1“4)-2,3,6-tri-O-acetyl-i-
D
- galactopyranosyl) - (1“4) -
- galactopyranosyl) -
-glucopyranoside
D
D
(10b).—Compound 9b (20 mg, 0.018 mmol)
was treated essentially as described in the
preparation of 10a, thus yielding 10b (16.3
1
mg, 65%); [h]2D2 +13° (c 1.0, CHCl3); H
NMR (CDCl3): l (assignments of aglycon
protons are shown in italic) 8.03–8.08 (m, 2
H, Ar-H), 7.55–7.62 (m, 1 H, Ar–H), 7.43–
7.50 (m, 3 H, Ar–H, NH), 5.93 (dt, 1 H, J 6.7,
13
CH2), 0.89 (t, 3 H, J 6.9 Hz, CH3); C NMR
(CDCl3): l 171.1, 171.0, 170.9, 170.8, 170.6,
170.2, 170.09, 170.08, 169.5, 165.5, 139.5,

198
H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
133.7, 130.3, 130.2, 128.9, 123.1, 101.5, 100.7,
99.9, 78.1, 76.8, 75.1, 73.7, 73.3, 73.0, 72.1,
72.0, 69.21, 69.15, 68.8, 67.7, 66.3, 63.9, 62.5,
61.8, 61.7, 50.5, 32.8, 32.4, 30.11, 30.09, 30.08,
30.02, 29.83, 29.78, 29.6, 29.1, 23.1, 21.4, 21.2,
21.13, 21.07, 20.99, 20.96, 20.9, 14.6; HRMS
Anal. Calcd for C63H87O27F3N4Na [M+Na]:
1411.5407. Found: 1411.5370.
acetyl-h-
O-acetyl-6-deoxy-6-trifluoroacetamido-i-
galactopyranosyl)-(1“4)-2,3,6-tri-O-acetyl-
i- -glucopyranoside (11a).—Compound 10a
D
-galactopyranosyl)-(1“4)-(2,3-di-
D
-
D
(7 mg, 0.005 mmol) was dissolved in a
pyridine–water (6:1, 6 mL) mixture and
cooled to 0 °C. H2S was bubbled through the
mixture for 1 h at 0 °C and the mixture was
kept under H2S for 44 h. Residual H2S was
removed with a stream of N2 for 1 h, the
mixture was concd with toluene, and the
residue was kept under vacuum overnight.
The residue was dissolved in CH2Cl2 (2 mL)
and N-(3-dimethylaminopropyl)-N%-ethylcar-
bodiimide (EDC, 20 mg, 0.1 mmol) and 1-
adamantaneacetic acid (20 mg, 0.1 mmol)
were added. The reaction mixture was stirred
at rt for 16 h and the solvent was removed.
The residue was chromatographed (1:1
EtOAc–heptane) to give 11a (5.8 mg, 75%);
(2S,3R,4E)-2-Azido-3-benzoyloxyoctadec-
4-enyl (2,3,4-tri-O-acetyl-6-deoxy-6-trifluoro-
acetamido - h -
(2,3,6 - tri - O - acetyl - i -
(1“4)-2,3,6-tri-O-acetyl-i-
D
- galactopyranosyl) - (1“4) -
- galactopyranosyl) -
-glucopyranoside
D
D
(10d).—Compound 9d (28 mg, 0.025 mmol)
was treated essentially as described in the
preparation of 10a, thus yielding 10d (22.5
1
mg, 64%); [h]2D2 +34° (c 1.0, CHCl3); H
NMR (CDCl3): l (assignments of aglycon
protons are shown in italic) 8.02–8.09 (m, 2
H, Ar–H), 7.55–7.62 (m, 1 H, Ar–H), 7.43–
7.50 (m, 2 H, Ar–H), 7.37–7.43 (m, 1 H, H-6¦
and NH), 5.93 (br dt, 1 H, J 6.7, 15.0 Hz,
H-5), 5.61 (dd, 1 H, J 4.1, 8.1 Hz, H-3),
5.50–5.60 (m, 1 H, H-4), 5.45 (br d, 1 H, J 3.2
Hz, H-4¦), 5.38 (dd, 1 H, J 3.4, 10.9 Hz,
H-3¦), 5.20 (t, 1 H, J 9.1 Hz, H-3), 5.08–5.17
(m, 2 H, H-2%,2¦), 5.02 (d, 1 H, J 3.5 Hz,
H-1¦), 4.96 (dd, 1 H, J 7.7, 9.2 Hz, H-2), 4.71
(dd, 1 H, J 2.1, 11.1 Hz, H-3%), 4.55 (d, 1 H, J
7.7 Hz, H-1%), 4.54 (d, 1 H, J 7.7 Hz, H-1),
4.37–4.51 (m, 3 H, incl. H-5¦), 4.17 (dd, 1 H,
J 6.8, 11.2 Hz), 4.07 (dd, 1 H, J 5.4, 12.0 Hz),
4.03 (br d, 1 H, J 2.0 Hz, H-4%), 3.75–3.98 (m,
5 H, incl. H-2, and H-4,6¦), 3.67 (ddd, 1 H, J
2.0, 5.4, 9.9 Hz, H-5 or H-5%), 3.60 (dd, 1 H, J
5.7, 10.3 Hz), 3.38 (br dt, 1 H, J 5.3, 13.6 Hz,
H-6¦), 2.19, 2.105, 2.09, 2.075, 2.06, 1.99 (6 s,
27 H, OAc), 1.20–1.45 (m, 24 H, CH2), 0.89
1
[h]2D2 +46° (c 0.5, CHCl3); H NMR (CDCl3):
l (assignments of aglycon protons are shown
in italic) 8.00–8.05 (m, 2 H, Ar–H), 7.53–7.64
(m, 2 H, Ar–H and NHCOCF3), 7.42–7.48
(m, 2 H, Ar–H), 5.90 (dt, 1 H, J 6.8, 15.2 Hz,
H-5), 5.69 (d, 1 H, J 9.0 Hz, NH) 5.61 (t, 1 H,
J 6.9 Hz, H-3), 5.53–5.56 (m, 1 H, H-4¦), 5.51
(br dd, 1 H, J 7.3, 15.3 Hz, H-4), 5.35 (dd, 1
H, J 3.3, 11.0 Hz, H-3¦), 5.23 (dd, 1 H, J 3.4,
11.0 Hz, H-2¦), 5.16 (t, 1 H, J 7.7 Hz, H-3),
5.09 (dd, 1 H, J 7.5, 10.5 Hz, H-2%), 4.98 (d, 1
H, J 3.2 Hz, H-1¦), 4.96 (dd, 1 H, J 6.4, 7.9
Hz, H-2), 4.74 (dd, 1 H, J 2.7, 10.5 Hz, H-3%),
4.58 (d, 1 H, J 7.3 Hz, H-1%), 4.56 (d, 1 H, J
6.2 Hz, H-1), 4.44–4.55 (m, 2 H, H-2 and
H-5¦), 4.38 (dd, 1 H, J 2.3, 11.9 Hz, H-6%),
4.19 (dd, 1 H, J 8.2, 10.8 Hz, H-6¦), 4.08–4.13
(m, 2 H, incl. H-4%), 4.04 (dd, 1 H, J 4.2, 10.4
Hz, H-6¦), 3.95 (dd, 1 H, J 6.0, 11.9 Hz, H-6%),
3.91 (br t, 1 H, J 8.2 Hz, H-4), 3.78–3.86 (m,
1 H), 3.74 (br d, 1 H, J 9.4 Hz), 3.61–3.69 (m,
2 H, incl. H-5%), 3.50–3.59 (m, 1 H), 1.90–2.16
(m, 32 H), 1.57–1.75 (m, 12 H), 1.20–1.40 (m,
13
(t, 3 H, J 6.9 Hz, CH3); C NMR (CDCl3): l
171.03, 170.95, 170.9, 170.8, 170.6, 170.4,
170.1, 170.0, 165.5, 157.9 (q), 139.5, 133.7,
130.3, 130.2, 128.9, 123.1, 116.2 (q), 101.1,
100.8, 99.9, 76.6, 75.1, 73.4, 73.1, 72.4, 71.8,
69.5, 69.4, 68.8, 68.1, 67.4, 63.9, 62.5, 62.1,
39.0, 32.8, 32.4, 30.11, 30.09, 30.08, 30.01,
29.83, 29.78, 29.6, 29.1, 23.1, 21.4, 21.2, 21.07,
21.06, 14.6; HRMS Anal. Calcd for
13
24 H), 0.89 (t, 3 H, J 6.9 Hz, CH3); C NMR
(CDCl3): l 171.1, 170.9, 170.6, 170.2, 169.4,
165.7, 138.0, 133.5, 130.7, 130.0, 128.8, 124.9,
101.1, 100.9, 100.2, 78.4, 76.0, 74.3, 73.7, 73.3,
72.9, 72.8, 72.0, 69.2, 69.0, 68.3, 68.2, 68.0,
67.4, 63.0, 60.9, 52.3, 51.3, 48.5, 43.0, 42.7,
41.2, 37.1, 33.2, 32.8, 32.4, 30.1, 29.9, 29.8,
29.7, 29.3, 29.0, 23.1, 21.3, 21.2, 21.1, 21.0,
C63H87O27F3N4Na
Found: 1411.5414.
[M+Na]:
1411.5407.
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
(benzoyloxy)-octadec-4-enyl (2,3,4,6-tetra-O-

H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
199
1
CHCl3); H NMR (CDCl3): l (assignments of
aglycon protons are shown in italic) 7.99–8.05
(m, 2 H, Ar–H), 7.54–7.60 (m, 1 H, Ar–H),
7.41–7.47 (m, 2 H, Ar–H), 6.66 (d, 1 H, J 9.1
Hz, NHCOCF3), 5.89 (br dt, 1 H, J 6.7, 15.2
Hz, H-5), 5.67 (d, 1 H, J 9.0 Hz, NH), 5.59
(br t, 1 H, J 6.9 Hz, H-3), 5.50 (br dd, 1 H, J
7.3, 15.3 Hz, H-4), 5.38 (dd, 1 H, J 4.1, 11.1
Hz, H-3¦), 5.19 (t, 1 H, J 9.1 Hz, H-3), 5.07
(dd, 1 H, J 7.7. 10.9 Hz, H-2%), 5.02 (d, 1 H, J
3.8 Hz, H-1¦), 4.88–4.96 (m, 2 H, H-2,2¦),
4.84 (br dd, 1 H, J 3.5, 9.0 Hz, H-4¦), 4.70
(dd, 1 H, J 2.4, 10.9 Hz, H-3%), 4.59–4.65 (m,
1 H, H-5¦), 4.51, 4.49 (d, 1 H each, J 7.5 and
7.6 Hz, H-1% or H-1), 4.46–4.53 (m, 1 H), 4.44
(dd, 1 H, J 6.4, 11.1 Hz), 4.35 (br d, 1 H, J
12.0 Hz), 4.26 (dd, 1 H, J 7.4, 11.1 Hz, H-6¦),
4.18 (dd, 1 H, J 4.1, 11.5 Hz, H-6¦), 4.12 (dd,
1 H, J 7.1, 11.0 Hz), 3.94–4.06 (m, 3 H, incl.
H-4%), 3.74–3.82 (m, 2 H, incl. H-4), 3.56–
3.68 (m, 2 H), 1.85–2.13, 1.55–1.75, 1.20–
1.40 (m, 68 H), 089 (t, 3 H, J 6.9 Hz, CH3);
13C NMR (CDCl3): l 171.1, 171.0, 170.9,
170.8, 170.6, 170.2, 170.0, 169.5, 165.6, 137.9,
133.5, 130.7, 130.0, 128.8, 125.0, 101.4, 100.7,
99.9, 78.1, 76.8, 74.3, 73.4, 73.3, 73.0, 72.2,
72.1, 69.2, 68.0, 67.7, 66.3, 62.6, 61.7, 52.3,
51.3, 50.6, 43.0, 37.1, 33.2, 32.8, 32.4, 30.1,
29.9, 29.8, 29.7, 29.3, 29.0, 23.1, 21.4, 21.23,
21.15, 21.1, 21.0, 20.9, 14.6; HRMS Anal.
Calcd for C75H105O28F3N2Na [M+Na]:
1561.6704. Found: 1561.6721.
14.6; HRMS Anal. Calcd for C75H105-
O28F3N2Na [M+Na]: 1561.6704. Found:
1561.6681.
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
(benzoyloxy) - octadec - 4 - enyl (3,4,6 - tri - O -
acetyl-2-deoxy-2-trifluoroacetamido-h-
actopyranosyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
-galactopyranosyl)-(1“4)-2,3,6-tri-O-acetyl-
i- -glucopyranoside (11b).—Compound 10b
D
-gal-
D
D
(16 mg, 0.012 mmol) was treated essentially as
described in the preparation of 11a, thus yield-
ing 11b (13.3 mg, 75%); [h]2D2 +29° (c 1.0,
1
CHCl3); H NMR (CDCl3): l (assignments of
aglycon protons are shown in italic) 8.01–8.06
(m, 2 H, Ar–H), 7.54–7.61 (m, 1 H, Ar–H),
7.41–7.49 (m, 3 H, Ar–H and NHCOCF3),
5.89 (br dt, 1 H, J 6.6, 15.3 Hz, H-5), 5.67 (d,
1 H, J 9.0 Hz, NH), 5.61 (br t, 1 H, J 6.8 Hz,
H-3), 5.57 (br d, 1 H, J 2.7 Hz, H-4¦), 5.50 (br
dd, 1 H, J 7.2, 15.4 Hz, H-4), 5.36 (dd, 1 H, J
3.1, 11.6 Hz, H-3¦), 5.23 (t, 1 H, J 9.1 Hz,
H-3), 5.12 (dd, 1 H, J 7.5, 10.8 Hz, H-2%), 5.07
(d, 1 H, J 3.5 Hz, H-1¦), 4.82–4.93 (m, 2 H,
H-2,3%), 4.57 (d, 1 H, J 7.5 Hz, H-1%), 4.47 (d,
1 H, J 7.7 Hz, H-1), 4.40–4.63 (m, 5 H, incl.
H-2¦, H-2), 4.09–4.20 (m, 2 H), 4.05 (br d, 1
H, J 2.4 Hz, H-4%), 3.88–4.05 (m, 3 H), 3.79 (t,
1 H, J 9.3 Hz, H-4), 3.75–3.84 (m, 1 H),
3.62–3.70 (m, 2 H), 1.85–2.19 (m, 32 H),
1.56–1.76 (m, 12 H), 1.18–1.40 (m, 24 H),
0.89 (t, 3 H, J 6.8 Hz, CH3); 13C NMR
(CDCl3): l 171.3, 171.2, 170.9, 170.8, 170.7,
170.6, 170.5, 170.2, 170.1, 169.4, 165.6, 137.8,
133.5, 130.7, 130.1, 128.8, 125.0, 100.6, 100.4,
99.3, 77.3, 76.9, 75.5, 74.3, 73.2, 72.7, 72.6,
72.5, 72.1, 69.6, 68.0, 67.8, 67.7, 67.2, 63.0,
60.7, 60.6, 52.3, 51.3, 50.3, 43.0, 37.1, 33.2,
32.8, 32.4, 30.11, 30.05, 29.9, 29.8, 29.7, 29.3,
29.0, 23.1, 21.3, 21.2, 21.12, 21.08, 21.00,
20.97, 20.95, 14.6; HRMS Anal. Calcd for
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
(benzoyloxy) - octadec - 4 - enyl (2,3,4 - tri - O -
acetyl-6-deoxy-6-trifluoroacetamido-h-
actopyranosyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
-galactopyranosyl)-(1“4)-2,3,6-tri-O-acetyl-
i- -glucopyranoside (11d).—Compound 10d
D
-gal-
D
D
(20 mg, 0.014 mmol) was treated essentially as
described in the preparation of 11a, thus yield-
ing 11d (18.6 mg, 84%); [h]2D2 +45° (c 1.2,
C75H105O28F3N2Na
Found: 1561.6681.
[M+Na]:
1561.6704.
1
CHCl3); H NMR (CDCl3): l (assignments of
(2S,3R,4E)-2-(1-Adamantaneacetamido)-3-
(benzoyloxy) - octadec - 4 - enyl (2,3,6 - tri - O -
aglycon protons are shown in italic) 7.99–8.06
(m, 2 H, Ar–H), 7.53–7.61 (m, 1 H, Ar–H),
7.39–7.48 (m, 3 H, Ar–H, NHCOCF3), 5.89
(br dt, 1 H, J 6.6, 15.3 Hz, H-5), 5.67 (d, 1 H,
J 9.1 Hz, NH), 5.60 (br t, 1 H, J 6.9 Hz, H-3),
5.45–5.54 (m, 1 H, H-4), 5.44 (br d, 1 H, J 3.3
Hz, H-4¦), 5.38 (dd, 1 H, J 3.4, 10.9 Hz,
H-3¦), 5.18 (t, 1 H, J 9.2 Hz, H-3), 5.11–5.17
acetyl-4-deoxy-4-trifluoroacetamido-h-
actopyranosyl)-(1“4)-(2,3,6-tri-O-acetyl-i-
-galactopyranosyl)-(1“4)-2,3,6-tri-O-acetyl-
i- -glucopyranoside (11c).—Compound 10c
D
-gal-
D
D
(13.3 mg, 0.01 mmol) was treated essentially
as described in the preparation of 11a, thus
yielding 11c (12.8 mg, 87%); [h]2D2 +24° (c 1.0,

200
H.C. Hansen, G. Magnusson / Carbohydrate Research 322 (1999) 190–200
Acknowledgements
(m, 1 H, H-2¦), 5.10 (dd, 1 H, J 7.7, 11.1 Hz,
H-2%), 5.01 (d, 1 H, J 3.4 Hz, H-1¦), 4.93 (dd,
1 H, J 7.9, 9.4 Hz, H-2), 4.70 (dd, 1 H, J 2.0,
11.0 Hz, H-3%), 4.51 (d, 1 H, J 7.8 Hz, H-1%),
4.49 (d, 1 H, J 7.8 Hz, H-1), 4.46–4.55 (m, 1
H, H-2), 4.32–4.46 (m, 3 H, incl. H-5¦), 4.18
(dd, 1 H, J 6.7, 11.2 Hz, H-6¦), 3.94–4.06
(m, 3 H, incl. H-4%), 3.74–3.86 (m, 3 H, incl.
H-4,6¦), 3.57–3.68 (m, 2 H), 3.32–3.42 (m, 1
H), 2.20–1.85 (m, 32 H), 1.55–1.75 (m, 12 H),
1.18–1.40 (m, 24 H), 0.89 (t, 3 H, J 6.8 Hz,
CH3); 13C NMR (CDCl3): 171.00, 170.95,
170.9, 170.8, 170.6, 170.3, 170.1, 165.6, 157.9
(q), 138.0, 133.5, 130.7, 130.0, 128.8, 125.0,
116.2 (q), 101.0, 100.8, 99.8, 76.9, 76.5, 74.2,
73.4, 73.2, 73.1, 72.4, 72.1, 69.5, 69.4, 68.1,
68.0, 67.4, 62.5, 62.1, 52.3, 51.2, 43.0, 39.0,
37.1, 33.2, 32.8, 32.4, 30.10, 30.05, 29.9, 29.8,
29.7, 29.3, 29.0, 23.1, 21.4, 21.22, 21.19,
21.15, 21.07, 14.6; HRMS Anal. Calcd for
This work was supported by the Swedish
Natural Science Research Council and the
National Institutes of Health (NIH, USA).
References
[1] H.C. Hansen, G. Magnusson, Carbohydr. Res., 322 (1999)
181–189.
[2] M. Mylvaganam, C.A. Lingwood, Biochem. Biophys. Res.
Commun., in press.
[3] H.C. Hansen, G. Magnusson, Carbohydr. Res., 322 (1999)
166–180.
[4] P.-G. Nyholm, G. Magnusson, Z. Zheng, R. Norel, B.
Binnington-Boyd, C.A. Lingwood, Chem. Biol., 3 (1996)
263–275.
[5] T.L. Lowary, O. Hindsgaul, Carbohydr. Res., 251 (1994)
33–67.
[6] R.R. Schmidt, W. Kinzy, Ad6. Carbohydr. Chem.
Biochem., 50 (1994) 21–123.
[7] (a) R.R. Schmidt, P. Zimmermann, Angew. Chem., Int. Ed.
Engl., 25 (1986) 725–726. (b) Y. Ito, M. Kiso, A.
Hasegawa, J. Carbohydr. Chem., 8 (1989) 285–294.
[8] K. Jansson, S. Ahlfors, T. Frejd, J. Kihlberg, G. Magnus-
son, J. Dahme´n, G. Noori, K. Stenvall, J. Org. Chem., 53
(1988) 5629–5647.
C75H105O28F3N2Na
Found: 1561.6696.
[M+Na]:
1561.6704.
.