A. Tuchinsky, U. Zeha6i / Chemistry and Physics of Lipids 92 (1998) 91–97
93
5.50 (d, 1H, J 15 Hz, benzylic CH2), 5.45 (m, 1H,
H-4, Sph, vinyl), 5.34 (d, 1H, J3%,4% 3.4 Hz, H-4%),
5.18 (t, 1H, J2,3 9.2 Hz, H-3), 5.09 (dd, 1H, J2%,3%
10.4 Hz, H-3%), 5.00 (ddꢀt, 1H, H-2%), 4.82 (t,
1H, H-2), 4.68 (d, 1H, J1%,2% 7.8 Hz, H-1%), 4.63 (d,
1H, J1,2 7.8 Hz, H-1), 4.49 (dd, 1H, J5,6b 11.6 Hz,
J6a,6b 1.6 Hz, H-6b), 4.23-4.10 (m, 1H, H-6a), 3.97
(s, 3H, OCH3), 3.87 (t, 1H, J4,5 9.2 Hz, H-4), 3.68
(m, 1H, H-5), 2.12, 2.08, 1.97, 1.91 (each s, each
3H, acetyl), 2.07-2.03 (m, 9H, 3 acetyls), 1.51 (m,
2H, Sph), 1.24 (ms, 22H, Sph), 0.88 (t, 3H, J17,18
6.6 Hz, CH3-18, Sph), lit. J1,2 7.8 Hz (Zehavi et
al., 1983). Anal. calc. for total sugar: 29.4%.
Found: 28.9%. MS: calc. 1177.8 (M). Found:
1176.9 (M-H)−.
1H NMR (CD3OD): l 8.71 (d, 1H, J3¦,5¦ 1.6 Hz,
H-3¦, aryl), 8.36 (dd, 1H, J5¦,6¦ 8.1 Hz, H-5¦, aryl),
7.88 (d, 1H, H-6¦, aryl), 5.76 (m, 1H, H-5, Sph,
vinyl), 5.56 (s, 1H, benzylic CH2), 5.56-5.54 (m,
1H, H-4, Sph, vinyl), 4.43 (d, 1H, J1%,2% 7.4 Hz,
H-1%), 4.37 (d, 1H, J1,2 7.9 Hz, H-1), 4.24-4.21 (m,
1H, Sph H-1b), 4.14 (t, 1H, J1,2 7.8 Hz, Sph
H-1a), 4.01 (s, 3H, OMe), 3.93-3.56 (m, 14H,
saccharide hydrogens), 3.33 (t, 1H, H-2), 2.10-
2.03 (m, 2H, Sph), 1.24-1.17 (ms, 22H, Sph), 0.88
(t, 3H, J17,18 6.6 Hz, CH3-18, Sph). Anal. calc. for
total sugar: 42.1%. Found: 42.9%. MS: calc.
860.4. Found: 861.4 (M-H)−.
2.3. (2S, 3R, 4E)-2-(4-Carboxymethyl-2-nitro-
Analytical data for compound 3: m.p. 63–68°C,
h3D1 −3.291.9° (c 4.4, methanol), Rf 0.36 (2:1,
ethyl acetate–petroleum ether), 1H NMR
(CD3OD): l 8.58 (s, 1H, H-3¦, aryl), 8.22 (d, 1H,
J5¦,6¦ 8.0 Hz, H-5¦, aryl), 7.75 (d, 1H, H-6¦, aryl),
5.68 (m, 1H, H-5, Sph, vinyl), 5.42 (s, 2H, ben-
zylic CH2), 5.48 (m, 1H, H-4, Sph, vinyl), 5.27 (d,
1H, J3%,4% 3.2 Hz, H-4%), 5.20 (m, 1H, H-3), 5.05
benzyloxycarbonylamino)-3-[4-O-(i-
pyranosyl)-i- -glucopyranosyloxy]-1-hydroxy-4-
octadecene (5)
D-galacto-
D
This compound was prepared in analogy to
compound 4 with the following amounts: com-
pound 3 (0.2 g, 0.17 mmol), sodium methoxide
(0.1 M,
3 ml) in methanol (20 ml) and
(m, 2H, H-2%, H-3%), 4.92 (t, 1H,
8.1 Hz, H-2),
dichlormethane (2 ml). Compound 5 (0. 14 g,
97%) was isolated as a white solid, h3D1 3.491.9°
(c 2.5, water), Rf 0.85 (1:1, methanol–chloro-
1,2
4.61 (d, 1H, J1%,2% 7.6 Hz, H-1%), 4.52 (d, 1H, J1,2
7.8 Hz, H-1), 4.94 (d, 1H, J5,6b 11.7 Hz, H-6b),
4.07-4.18 (m, 1H, H-6a), 3.88 (s, 3H, OCH3), 3.79
(t, 1H, J4,5 9.6 Hz, H-4), 3.60 (m, 1H, H-5), 2.04,
2.03, 1.91, 1.84, (each s, each 3H, acetyl), 2.01-
1.94 (m, 9H, 3 acetyls), 1.53 (m, 2H, Sph), 1.24-
1.17 (ms, 22H, Sph), 0.88 (t, 3H, J17,18 6.6 Hz,
CH3-18, Sph), lit. J1,2 7.8 Hz (Zehavi et al., 1983).
Anal. calc. for total sugar: 29.4%. Found: 29.0%.
MS: calc. 1177.8 (M). Found: 1176.9 (M-H)−.
1
form), H NMR (CD3OD): l 8.72 (d, 1H, J3¦,5¦
1.5 Hz, H-3¦, aryl), 8.36 (dd, 1H, J5¦,6¦ 8.1 Hz,
H-5¦, aryl), 7.90 (d, 1H, H-6¦, aryl), 5.78-5.74 (m,
1H, H-5, Sph, vinyl), 5.62 (s, 2H, benzylic CH2),
4.55 (d, 1H, J1%,2%7.8 Hz, H-1%), 4.41 (d, 1H, J1,2 7.5
Hz, H-1), 4.01-3.34 (m, 14H, saccharide hydro-
gens), 3.25 (mꢀt, 1H, H-2), 2.10-2.03 (ms, 2H,
Sph), 1.33-1.28 (ms, 22H, Sph), 0.94 (m, 3H,
CH3-18, Sph). Anal. calc. for total sugar: 42.1%.
Found: 42.9%. MS: calc. 860.4. Found: 861.4
(M-H)−.
2.2. (2S, 3R, 4E)-2-(4-Carboxymethyl-2-nitro-
benzyloxycarbonylamino)-1-[4-O-(i-
pyranosyl)-i- -glucopyranosyloxy]-3-hydroxy-4-
octadecene (4)
D-galacto-
D
2.4. (5-Acetamido-3,5-dideoxy-
acto-2-nonulopyranosylonic acid)-(2-3)-i-
galactopyranosyl-(1-4)-i- -glucopyranosyl-
D-glycero-h-D-gal-
D
-
Compound 2 (0.5 g, 0.42 mmol) was treated
with sodium methoxide (0.1 M, 7 ml) in methanol
(53 ml) and dichlormethane (5 ml) for 25 min.
The solution was neutralized with a cation ex-
change resin (Amberlite IR-120, H+-form),
filtered and concentrated to yield compound 4
(0.35 g, 96%) as a white solid, h3D1 3.791.9°C (c
3.1, water), Rf 0.9 (1:1, methanol–chloroform),
D
oxy-(1-1)-(2S, 3R, 4E)-2-(4-carboxymethyl-2-
nitrobenzyl-oxycarbonylamino)-3-hydroxy-4-
octadecene (6)
An incubation mixture (100 vl) containing
compound 4 (86 vg, 100 nmol), CMP-NeuNAc
(60 vg, 94 nmol) including CMP-[14C]-NeuNAc