L. F. Tietze et al.
FULL PAPER
The residue was dissolved in Ac2O (0.3 mL), pyridine (0.6 mL), and CH2Cl2
(5 mL) and DMAP (10 mg) was added. After stirring for 14 h the solution
was concentrated in vacuo. The residue was purified by flash chromatog-
raphy (EtOAc) to yield 21 (282 mg, 97%): [a]2D0 À6.68 (c 0.5 in CHCl3);
Rf 0.19 (EtOAc); 1H NMR (500 MHz, CDCl3): d 0.01 (s, 9H, SiMe3),
0.93 (m, 2H, CH2SiMe3), 1.87 (dd, J 10.5, 13.5 Hz, 1H, 3c-Hax), 1.90 (s,
3H, CH3CON), 2.03, 2.06, 2.08, 2.09, 2.13, 2.15 (s, 27H, 9CH3CO), 2.60 (dd,
J 5.5, 13.5 Hz, 1H, 3c-Heq), 3.44 (d, J 11.5 Hz, 1H, 1c-Hax), 3.59 (dd, J
7.5, 10.5 Hz, 1H, 2b-H), 3.52 ± 3.58 (m, 1H, OCH2CH2SiMe3), 3.64 (dt, J
3.5, 10.0 Hz, 1H, 5a-H), 3.71 (dd, J 3.0, 10.5 Hz, 1H, 3b-H), 3.81 (t, J
9.5 Hz, 1H, 4-H), 3.80 ± 3.91 (m, 4H, 5b-H, 5c-H, 6b-Ha, 6c-H), 3.89 (d, J
11.5 Hz, 1H, 1c-Heq), 3.92 ± 3.99 (m, 1H, OCH2CH2SiMe3), 4.02 ± 4.13 (m,
2H, 6a-Ha, 6b-Hb), 4.10 (q, J 6.0 Hz, 1H, 9c-Ha), 4.35 (J 7.5 Hz, 1H, 1b-
H), 4.38 ± 4.43 (m, 2H, 6a-Hb, 9c-Hb), 4.49 (d, J 8.0 Hz, 1H, 1a-H), 4.88
(dd, J 8.0, 9.5 Hz, 1H, 2-H), 5.21 (t, J 9.5 Hz, 1H, 3a-H), 5.15 ± 5.23 (m,
2H, 4c-H, 8c-H), 5.25 (dd, J 2.0, 6.5 Hz, 1H, 7c-H), 5.29 (dd, J 1.5,
3.0 Hz, 1H, 4b-H), 5.32 (d, J 9.0 Hz, 1H, NH); 13C NMR (125.7 MHz,
CDCl3): d À1.45 (SiMe3), 17.89 (CH2SiMe3), 20.56, 20.61, 20.73, 20.76,
20.88, 20.91, 20.93, 23.28 (10CH3CO), 34.18 (C-3c), 50.39 (C-5c), 61.43,
62.31, 62.43, 62.52, 68.11 (C-1c, C-6a, C-6b, C-9c, OCH2CH2SiMe3), 66.75,
68.00, 68.90, 70.49, 71.49, 71.66, 71.84, 72.59, 72.66, 73.19, 73.58, 77.19 (C-2a,
C-3a, C-4a, C-5a, C-2b, C-3b, C-4b, C-5b, C-4c, C-6c, C-7c, C-8c), 96.74 (C-
2c), 100.1 (C-1b), 102.0 (C-1a), 169.6, 169.9, 167.0, 170.4, 170.6, 170.7
(10CH3CO); IR (KBr): nÄ 1750, 1372, 1234, 1160, 1048, 840 cmÀ1; MS
molecular sieves (4 ) in CH2Cl2 (5 mL) was stirred for 2 h at rt. The
solution was cooled to À408C and BF3 ´ OEt2 (30 mL) was added. The
mixture was allowed to warm up to À208C within 1 h and the reaction was
quenched by addition of triethylamine (0.2 mL). After filtration the
solution was concentrated in vacuo and the residue purified by flash
chromatography (EtOAc) to yield 26 (86 mg, 66%): [a]2D0 À7.48 (c 0.5
in CHCl3, b-anomer (C-2c)); Rf 0.33 (a-anomer (C-2c)), 0.29 (b-anomer
(C-2c)) (EtOAc); 1H NMR (500 MHz, CDCl3, a-anomer (C-2c)): d 0.88
(t, J 7.0 Hz, 3H, CH'3), 1.20 ± 1.40 (m, 22H, CH'2), 1.90 ± 2.15 (10s, 30H,
10CH3CO), 2.50 (dd, J 5.5, 13.5 Hz, 1H, 3c-Heq), 3.45 (d, J 11.5 Hz, 1H,
1c-Hax), 3.56 ± 3.61 (m, 2H, 2b-H, 1'-H'a), 3.65 (m, 1H, 5a-H), 3.71 (dd, J
3.0, 10.5 Hz, 1H, 3b-H), 3.83 (t, J 10.0 Hz, 1H, 4a-H), 3.89 (d, J 11.5 Hz,
1H, 1c-Heq), 3.80 ± 3.96 (m, 4H, 5b-H, 6b-Ha, 1'-Hb, 2'-Ha), 4.02 ± 4.09 (m,
2H, 6a-Ha, 6b-Hb), 4.10 (q, J 6.5 Hz, 1H, 9c-Ha), 4.34 (d, J 8.0 Hz, 1H,
1b-H), 4.35 ± 4.42 (m, 2H, 6a-Hb, 9c-Hb), 4.52 (d, J 8.0 Hz, 1H, 1a-H),
4.94 (dd, J 8.0, 10.0 Hz, 1H, 2a-H), 5.16 ± 5.23 (m, 3H, 3a-H, 4c-H, 8c-H),
5.25 (dd, J 2.0, 6.5 Hz, 1H, 7c-H), 5.29 (dd, J 1.5, 3.0 Hz, 1H, 4b-H),
5.31 (d, J 9.0 Hz, 1H, NH), 5.53 (ddt, J 1.5, 8.0, 15.0 Hz, 1H, 4'-H), 5.59
(dd, J 4.0, 8.0 Hz, 1H, 3'-H), 5.92 (dt, J 6.5, 15.0 Hz, 1H, 5'-H), 7.44 (m,
2H, OBz), 7.56 (m, 1H, OBz), 8.03 (m, 2H, OBz); 1H NMR (500 MHz,
CDCl3, b-anomer (C-2c)): d 0.88 (t, J 7.0 Hz, 3H, CH'3), 1.20 ± 1.42 (m,
22H, CH'2), 1.90 ± 2.16 (10s, 30H, 10CH3CO), 1.96 (dd, J 5.5, 12.5 Hz,
1H, 3c-Heq), 3.39 (dd, J 8.0, 10.0 Hz, 1H, 2b-H), 3.42 (d, J 12.0 Hz, 1H,
1c-Hax), 3.58 (dd, J 6.0, 10.5 Hz, 1H, 1'-Ha), 3.64 (ddd, J 2, 5, 10.0 Hz,
1H, 5a-H), 3.76 ± 4.10 (m, 11H), 4.23 (dd, J 5.5, 12.0 Hz, 1H), 4.39 (dd,
J 2.0, 12.0 Hz, 1H), 4.50 (d, J 8.0 Hz, 1H, 1b-H), 4.64 (d, J 7.5 Hz, 1H,
1a-H), 4.73 (dd, J 3.0, 12.5 Hz, 1H), 4.97 (dd, J 8.0, 9.5 Hz, 1H), 5.10
(m, 1H), 5.20 ± 5.26 (m, 2H), 5.31 (d, J 10.5 Hz, 1H, NH), 5.36 ± 5.43 (m,
2H), 5.56 (ddt, J 1.5, 7.5, 15.0 Hz, 1H, 4'-H), 5.62 (dd, J 4.0, 8.5 Hz, 1H,
3'-H), 5.92 (dt, J 6.5, 15.0 Hz, 1H, 5'-H), 7.45 (m, 2H, OBz), 7.57 (m, 1H,
OBz), 8.04 (m, 2H, OBz); 13C NMR (125.7 MHz, CDCl3, a-anomer (C-
2c)): d 14.12 (C'H3), 20.65, 20.76, 20.91, 20.96, 23.33 (10CH3CO), 22.86,
28.73, 29.16, 29.35, 29.39, 29.59, 29.65, 31.92, 32.38 (12CH2), 50.46 (C-5c),
61.45, 62.30, 63.50, 66.75, 67.99, 68.12, 68.31, 68.87, 70.45, 71.51, 71.71, 72.65,
72.82, 72.98, 73.57, 74.66, 76.49, 96.75 (C-2c), 100.4 (C-1b), 102.1 (C-1a),
(DCI): m/z (%): 1098.3 [MNH3H] ; C46H69NO26Si (1080.13): calcd C
51.15, H 6.44; found: C 51.10, H 6.11.
2'-(Trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-[4,6-di-O-acetyl-3-O-(4,7,8,9-
tetra-O-acetyl-5-acetamido-3,5-dideoxy-d-glycero-a-d-galacto-2-nonulo-
pyranosyl-1c-ol)-b-d-galactopyranosyl]-b-d-glucopyranoside (23): Sodium
borohydride (25.0 mg, 389 mmol) was added at 08C to a solution of 22
(100 mg, 82.2 mmol) in THF (5 mL). After stirring at 08C for 4 h the
reaction was quenched with saturated NH4Cl (10 mL) and the aqueous
layer was extracted with CH2Cl2 (3 Â 10 mL). After drying over MgSO4 the
organic layer was concentrated in vacuo. The residue was purified by flash
chromatography (EtOAc) to give 23 (62.0 mg, 62%): Rf 0.22 (EtOAc);
1H NMR (500 MHz, CDCl3): d 0.01 (s, 9H, SiMe3), 1.02 (m, 2H,
CH2SiMe3), 1.85 (dd, J 11, 13 Hz, 1H, 3c-Hax), 1.98 ± 2.09 (7s, 21H,
CH3CO), 2.31 (dd, J 5.0, 13.0 Hz, 1H, 3c-Heq), 3.40 (dd, J 8.0, 9.0 Hz,
1H), 3.49 ± 3.67 (m, 8H), 3.73 (dd, J 6.0, 11.0 Hz, 1H), 3.80 (dd, J 1.5,
10.5 Hz, 1H), 3.85 (t, J 10.0 Hz, 1H), 3.91 ± 4.05 (m, 5H), 4.11 (dd, J 3.5,
9.5 Hz, 1H), 4.30 (dd, J 2.5, 12.5 Hz, 1H), 4.38 (d, J 8.0 Hz, 1H, 1b-H),
4.58 (d, J 12.0 Hz, 1H, OCH2Bn), 4.66 (d, J 11.5 Hz, 1H, OCH2Bn),
4.73 (d, J 7.5 Hz, 1H, 1-H), 4.87 ± 4.95 (m, 3H, 3 OCH2Bn), 5.05 (dd, J
1.5, 3.0 Hz, 1H, 4b-H), 5.09 (m, 1H, 8c-H), 5.22 (dd, J 1.5, 8.0 Hz, 1H, 7c-
H), 5.31 (m, 1H, 4b-H), 5.34 (d, J 9.5 Hz, 1H, NH), 7.2 ± 7.36 (m, 15H,
122.6 (C ), 128.5, 129.7 (o-, m-Ph-C), 129.9 (i-Ph), 133.2 (p-Ph), 139.0 (C ),
165.1, 170.3, 170.4 (10CH3CO); 13C NMR (125.7 MHz, CDCl3, b-anomer
(C-2c)): d 14.12 (C'H3), 20.69, 20.71, 20.74, 20.78, 20.86, 20.90, 21.03, 23.19
(10CH3CO), 22.70, 28.75, 29.17, 29.36, 29.41, 29.60, 29.66, 29.67, 29.69,
31.93, 32.39 (12CH2), 36.40 (C-3c), 49.48 (C-5c), 61.21, 62.17, 62.43, 68.34,
71.14 (C-1c, C-6a, C-6b, C-9c, C-1'), 63.54, 66.91, 67.78, 68.57, 68.71, 70.36,
70.44, 71.26, 71.46, 72.90, 73.20, 74.48, 74.70, 96.07 (C-2c), 100.5, 101.2 (C-
1a, C-1b), 122.7 (C ), 128.5, 129.7 (o-, m-Ph-C), 130.0 (i-Ph-C), 133.2 (p-Ph-
C), 139.0 (C ), 165.1, 169.6, 169.9, 170.0, 170.1, 170.3, 170.6, 170.7, 170.8,
171.0 (10CH3CO); IR (KBr, b-anomer (C-2c)): nÄ 2928, 2108, 1748, 1690,
1372, 1232, 1176, 1110, 1068, 1042 cmÀ1; MS (DCI): m/z (%): 1408.9
Ph); MS (DCI): m/z (%): 1260.2 (100) [MNH3H] .
[MNH3H] ; C66H94N4O28 (1391.48).
2,3,6-Tri-O-acetyl-4-O-[4,6-di-O-acetyl-3-O-(4,7,8,9-tetra-O-acetyl-5-acet-
amido-1,3,5-trideoxy-d-glycero-a-d-galacto-2-nonulopyranosyloyl-1c !
2b-pyranosyl)-b-d-galactopyranosyl]-b-d-glucopyranosyl trichloroacetimi-
date (25): Trifluoroacetic acid (2 mL) was added to a solution of 21
(110 mg, 0.102 mmol) in dry CH2Cl2 (1 mL). After stirring for 0.5 h at rt the
solution was concentrated in vacuo, diluted with toluene (5 mL), and
concentrated in vacuo again. The residue was purified by column
chromatography (EtOAc/MeOH 10:1). The filtrate was concentrated and
dried in vacuo for 3 h and then dissolved in CH2Cl2 (5 mL). The solution
was cooled to 08C and trichloroacetonitrile (0.34 mL) and DBU (13 mL)
were added. After stirring for 1 h at 08C the solution was concentrated in
vacuo. The residue was purified by flash chromatography (EtOAc/MeOH
10:1) to yield 25 (106.5 mg, 93%): Rf 0.55 (EtOAc/MeOH 10:1); 1H NMR
(500 MHz, CDCl3, both anomers (C-2c)): d 1.91 ± 2.16 (s, 30H,
10CH3CO), 2.51 (dd, J 5.5, 13.5, 1H, 3c-Heq (b-anomer)), 2.57 (dd, J
5.5, 13.5 Hz, 1H, 3c-Heq (a-anomer)), 3.43 (d, J 11.5 Hz, 1H, 1c-Hax), 4.39
(d, J 8.0 Hz, 1H, 1b-H (b-anomer)), 4.64 (d, J 8.0 Hz, 1H, 1b-H (a-
anomer)), 6.49 (d, J 3.5 Hz, 1H, 1a-H (b-anomer)), 6,50 (d, J 3.5 Hz,
(2S,3R,4E)-3-Benzoyloxy-2-(octadecanamido)octadec-4-enyl 2,3,6-tri-O-
acetyl-4-O-[4,6-di-O-acetyl-3-O-(4,7,8,9-tetra-O-acetyl-5-acetamido-1,3,5-
trideoxy-d-glycero-a-d-galacto-2-nonulopyranosyloyl-1c ! 2b-pyranosyl)-
b-d-galactopyranosyl]-b-d-glucopyranoside (27): Di(thiophenyl)tin(ii)
(28 mL, 270 mmol) and triethylamine (37 mL, 270 mmol) were successively
added at 08C to a solution of 26 (75 mg, 54 mmol) in CH2Cl2 (5 mL). After
stirring for 4 h at rt ethyl acetate (30 mL) was added and the solution was
washed with 0.1n NaOH (3 Â 20 mL) and water (20 mL). The combined
aqueous layers were extracted with CH2Cl2 (2 Â 5 mL) and the combined
organic layers were washed with water (5 mL). The organic layer was dried
over MgSO4 and concentrated in vacuo. After drying in vacuo for 1 h the
residue was dissolved in CH2Cl2 (5 mL) and stearic acid (77 mg, 270 mmol)
and EDC (52 mg, 270 mmol) were added. The reaction was stirred for 2 h at
rt and diluted with CH2Cl2 (20 mL). The solution was washed successively
with 8n HCl (8 mL) and saturated NaHCO3 solution. The solution was
dried over MgSO4 and concentrated in vacuo. The residue was purified by
flash chromatography (EtOAc) to give 27 (64.5 mg, 73%): [a]2D0 4.88
(c 0.5 in CHCl3, b-anomer (C-2c)); Rf 0.27 (EtOAc); 1H NMR
(500 MHz, CDCl3, a-anomer (C-2c)): d 0.88 (t, J 7.0 Hz, 6H, CH'3),
1.20 ± 1.40 (m, 52H, CH'2), 1.65 (m, 2H, 6'-Ha,b), 1.90 ± 2.15 (10s, 30H,
10CH3CO), 2.49 (dd, J 5.5, 13.5 Hz, 1H, 3c-Heq), 3.43 (d, J 11.5 Hz, 1H,
1c-Hax), 3.56 ± 3.61 (m, 2H, 2b-H, 1'-H), 3.64 (m, 1H, 5a-H), 3.70 (dd, J
3.0, 10.5 Hz, 1H, 3b-H), 3.78 (t, J 9.5 Hz, 1H, 4a-H), 3.80 ± 3.93 (m, 3H),
4.00 ± 4.12 (m, 5H), 4.23 (dd, J 2.0, 12.0 Hz, 1H), 4.28 (dd, J 4.0,
1H, 1b-H (a-anomer)), 8.66 (s, 1H), 8.70 (s, 1H, C NH (b-anomer));
C43H57N2O26Si3 (1024.28).
(2S,3R,4E)-2-Azido-3-(benzoyloxy)octadec-4-enyl 2,3,6-tri-O-acetyl-4-O-
[4,6-di-O-acetyl-3-O-(4,7,8,9-tetra-O-acetyl-5-acetamido-1,3,5-trideoxy-d-
glycero-a-d-galacto-2-nonulopyranosyloyl-1c ! 2b-pyranosyl)-b-d-galac-
topyranosyl]-b-d-glucopyranoside (26):
A solution of 25 (106 mg,
94,3 mmol), 2-azido-3-O-benzoylsphingosine (125 mg, 0.291 mmol), and
2806
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
0947-6539/00/0615-2806 $ 17.50+.50/0
Chem. Eur. J. 2000, 6, No. 15