J. Lindberg et al. / Tetrahedron 58 +2002) 5109±5117
5115
74.9, 74.8, 74.6, 73.8, 73.7, 73.2, 73.0, 72.4, 72.3, 69.7,
69.3, 68.0%2C), 50.5, 44.7; Anal. calcd for C 64H68O12: C,
74.7; H, 6.7. Found: C, 74.5; H, 6.5.
J11.6 Hz, CH2Ph), 4.10%1H, dd, J10.1, 3.4 Hz, H-200),
4.09 %1H, d, J2.2 Hz, H-400), 4.07 %1H, dd, J10.1, 2.2 Hz,
0
H-300), 4.02 %1H, d, J3.0Hz, H-4 ), 4.01 %1H, dd, J10.8,
4.9 Hz, H-1a), 3.97 %1H, dd, J9.3, 7.9 Hz, H-6a0), 3.71
%1H, dd, J10.8, 5.2 Hz, H-1b), 3.65 %1H, dd, J10.1,
7.5 Hz, H-20), 3.62 %1H, dd, J10.8, 6.0 Hz, H-3a), 3.60
%1H, dd, J10.8, 4.5 Hz, H-3b), 3.54 %1H, dd, J9.3,
4.1.10. 1-O-Hexadecyl-3-O-[2,3,4,6-tetra-O-benzyl-a-d-
galactopyranosyl-*1!4)-2,3,6-tri-O-benzyl-b-d-galacto-
pyranosyl]-sn-glycerol *19). To a stirred solution of 18
0
%85 mg,
0.083 mmol)
and
hexadecanol
%40 mg,
8.6 Hz, H-6a00), 3.50%1H, dd, J9.3, 6.0Hz, H-6b ), 3.45
0
0.16 mmol) in dichloromethane %1.5 mL) was added
BF3´Et2O %0.020 mL, 10% in dichloromethane). After
19 h, the mixture was diluted with CH2Cl2 and washed
with aqueous NaHCO3 %sat.). The organic layer was dried,
®ltered and concentrated. FC %petroleum ether 65±75/
EtOAc 10:1!2:1) gave 19 %66 mg, 0.052 mmol, 63%) as
a colorless syrup. Rf 0.29 %petroleum ether 650±75/EtOAc
3:1); [a]D137.1 %c 1.0, CHCl3); IR nmax cm21 1099, 1454,
%1H, dd, J7.9, 6.0Hz, H-5 ), 3.41 %1H, ddd, J9.3, 6.7,
6.7 Hz, CH2CH2O), 3.36 %1H, dd, J10.1, 3.0 Hz, H-30),
3.34 %1H, ddd, J9.3, 6.7, 6.7 Hz, CH2CH2O), 3.23 %1H,
dd, J8.6, 4.9 Hz, H-6b00), 2.31±2.22 %2H, m), 1.60±1.55
%2H, m), 1.52±1.48 %2H, m), 1.32±1.21 %50H, br), 0.88 %6H,
t, J7.1 Hz); 13C %75 MHz, CDCl3), d 173.3, 139.0±138.1,
128.4±127.3, 104.2, 100.4, 80.7, 79.0, 78.7, 76.5, 75.0,
74.9, 74.8, 74.5, 73.7, 73.6, 73.2, 73.0, 72.4, 72.3, 71.6,
71.3, 69.3 %2C), 68.2, 68.0, 67.8, 34.4, 31.9, 29.7±29.6,
29.5, 29.3, 29.1, 26.1, 25.0, 22.7, 14.1; Anal. calcd for
C96H132O14: C, 76.4; H, 8.8. Found: C, 76.4; H, 8.8.
1
2854, 1924; NMR: H %600 MHz, CDCl3), d 7.39±7.16
00
%35H, m), 5.00 %1H, d, J3.0Hz, H-1 ), 4.91 %1H, d,
J11.2 Hz, CH2Ph), 4.88 %1H, d, J12.0Hz, C H2Ph),
4.85 %1H, d, J10.8 Hz, CH2Ph), 4.80%1H, d, J11.2 Hz,
CH2Ph), 4.79±4.75 %3H, m, CH2Ph), 4.66 %1H, d,
J11.6 Hz, CH2Ph), 4.55 %1H, d, J11.2 Hz, CH2Ph),
4.52 %1H, d, J12.7 Hz, CH2Ph), 4.41 %1H, dd, J9.0,
4.7 Hz, H-500), 4.35 %1H, d, J7.5 Hz, H-10), 4.21 %2H, s,
CH2Ph), 4.15 %1H, d, J11.2 Hz, CH2Ph), 4.13 %1H, d,
J11.2 Hz, CH2Ph), 4.11±4.06 %3H, m, H-200, 300, 400),
4.1.12. 3-O-[a-d-Galactopyranosyl-*1!4)-b-d-galacto-
pyranosyl]-1-O-hexadecyl-sn-glycerol *2a). A mixture of
19 %14 mg, 0.011 mmol) and 10% Pd on carbon %2 mg) in
EtOAc/MeOH 1:1 %2 mL) was stirred under H2 %1 atm) for
22 h, ®ltered through Celite and concentrated. FC %CHCl3/
MeOH 5:1) gave 2a %7 mg, 0.011 mmol, 100%) as a white
solid. Rf 0.05 %CHCl3/MeOH 5:1); mp 2108C %dec.) %from
MeOH/EtOAc); [a]D135.3 %c 0.7, CHCl3/MeOH 5:1); IR
0
4.00 %1H, d, J3.0Hz, H-4 ), 4.01±3.98 %1H, m, H-2),
3.91 %1H, dd, J9.3, 7.1 Hz, H-6a0), 3.89 %1H, dd,
J11.2, 3.7 Hz, H-1a), 3.76 %1H, dd, J11.2, 6.7 Hz,
H-1b), 3.68 %1H, dd, J10.1, 7.5 Hz, H-20), 3.55 %1H, dd,
1
nmax cm21 1075, 1468, 1597, 2850, 2918, 3387; NMR: H
%600 MHz, CDCl3/CD3OD 5:1), d 5.01 %1H, d, J3.7 Hz,
0
0
J9.0, 8.4 Hz, H-6a00), 3.54 %1H, dd, J9.3, 6.0Hz, H-6b ),
H-100), 4.29 %1H, d, J7.0Hz, H-1 ), 4.17 %1H, dd, J7.3,
0
3.50%1H, dd, J7.1, 6.0Hz, H-5 ), 3.46 %1H, dd, J9.7,
4.4 Hz, H-500), 4.01 %1H, dd, J2.7, 1.3 Hz, H-40), 3.96±
3.93 %1H, m, H-2), 3.94 %1H, d, J3.1 Hz, H-400), 3.86
%1H, dd, J11.0, 6.2 Hz, H-1a), 3.86±3.81 %3H, m, H-200,
6a0, 6a00), 3.80%1H, dd, J7.1, 3.1 Hz, H-300), 3.77 %1H, dd,
J11.4, 5.5 Hz, H-6b0), 3.74±3.71 %2H, m, H-1b, 6b00),
3.65±3.63 %1H, m, H-50), 3.53 %1H, dd, J10.1, 2.7 Hz,
H-30), 3.50%1H, dd, J10.1, 7.0 Hz, H-20), 3.50±3.46
%2H, m, H-3a, 3b), 3.46 %2H, dd, J6.8, 6.8 Hz,
CH2CH2O), 1.59±1.55 %2H, m), 1.33±1.24 %26H, br), 0.88
%3H, t, J7.0Hz); 13C %75 MHz, CDCl3/CD3OD 5:1), d
104.1, 101.8, 79.5, 74.3, 73.6, 72.1, 72.1, 72.0, 71.8 %2C),
70.1, 70.0, 69.5, 69.4, 62.2, 60.1, 32.1, 29.9±29.8, 29.7,
29.6, 29.5, 28.3, 26.2, 22.8, 14.2; Anal. calcd for
C31H60O13: C, 58.1; H, 9.4. Found: C, 57.9; H, 9.4.
5.6 Hz, H-3a), 3.43 %1H, dd, J9.7, 5.6 Hz, H-3b), 3.42±
3.39 %2H, m, CH2CH2O), 3.38 %1H, dd, J10.1, 3.0 Hz,
H-30), 3,25 %1H, dd, J8.4, 4.7 Hz, H-6b00), 1.56±1.52
%2H, m), 1.31±1.21 %26H, br), 0.88 %3H, t, J7.1 Hz); 13C
%75 MHz, CDCl3), d 139.0±138.0, 128.4±127.4, 104.6,
100.4, 80.9, 79.0, 78.9, 76.6, 75.2, 74.9, 74.8, 74.5, 73.8,
73.7, 73.4, 73.2, 73.1, 72.3 %2C), 71.7, 71.6, 69.7, 69.4, 68.0,
67.9, 31.9, 29.7±29.6, 29.5, 29.4, 26.1, 22.7, 14.1; Anal.
calcd for C80H102O13: C, 75.6; H, 8.1. Found: C, 75.5; H, 8.2.
4.1.11. 3-O-Hexadecyl-2-O-palmitoyl-3-O-[2,3,4,6-tetra-
O-benzyl-a-d-galactopyranosyl-*1!4)-2,3,6-tri-O-benzyl-
b-d-galactopyranosyl]-sn-glycerol *20). A solution of 19
%48 mg, 0.038 mmol), palmitic acid %19 mg, 0.074 mmol),
dicyclohexylcarbodiimide %16 mg, 0.078 mmol) and 4-
%dimethylamino)pyridine %1 mg, 0.01 mmol) in CH2Cl2
%1 mL) was stirred for 22 h, ®ltered through Celite and
concentrated. FC %petroleum ether 65±75/EtOAc 10:1)
gave 20 %47 mg, 0.031 mmol, 82%) as a colorless syrup.
Rf 0.70 %petroleum ether 65±75/EtOAc 3:1); [a]D131.8
%c 0.8, CHCl3); IR nmax cm21 1100, 1454, 1733, 1739, 2853,
2921; NMR: 1H %600 MHz, CDCl3), d 7.38±7.14 %35H, m),
5.21±5.18 %1H, m, H-2), 5.02 %1H, d, J3.4 Hz, H-100), 4.90
%1H, d, J11.2 Hz, CH2Ph), 4.89 %1H, d, J11.2 Hz,
CH2Ph), 4.89 %1H, d, J11.6 Hz, CH2Ph), 4.78 %1H, d,
J12.7 Hz, CH2Ph), 4.79±4.75 %3H, m, CH2Ph), 4.69
%1H, d, J12.0Hz, C H2Ph), 4.54 %1H, d, J11.2 Hz,
CH2Ph), 4.53 %1H, d, J12.7 Hz, CH2Ph), 4.41 %1H, dd,
J9.3, 4.9 Hz, H-500), 4.31 %1H, d, J7.5 Hz, H-10), 4.26
%1H, d, J11.6 Hz, CH2Ph), 4.21 %1H, d, J12.0Hz,
CH2Ph), 4.14 %1H, d, J11.6 Hz, CH2Ph), 4.12 %1H, d,
4.1.13. 3-O-[a-d-Galactopyranosyl-*1!4)-b-d-galacto-
pyranosyl]-1-O-hexadecyl-2-O-palmitoyl-sn-glycerol *2b).
A mixture of 20 %26 mg, 0.017 mmol) and 10% Pd on
carbon %4 mg) in EtOAc/MeOH 1:1 %2 mL) was stirred
under H2 %1 atm) for 24 h, ®ltered through Celite and
concentrated. FC %CHCl3/MeOH 10:1!5:1) gave 2b
%14 mg, 0.016 mmol, 92%) as a white solid. Rf 0.26
%CHCl3/MeOH 5:1); mp 200±2038C %from EtOAc);
[a]D130.8 %c 1.3, CHCl3/MeOH 10:1); IR nmax cm21
1
1075, 1470, 1733, 2849, 2916, 3344; NMR: H %600 MHz,
CDCl3/CD3OD 5:1), d 5.19±5.16 %1H, m, H-2), 5.01 %1H, d,
J3.7 Hz, H-100), 4.26 %1H, d, J7.7 Hz, H-10), 4.17 %1H,
dd, J7.7, 4.7 Hz, H-500), 4.02 %1H, d, J3.1 Hz, H-40), 3.96
%1H, dd, J11.0, 5.9 Hz, H-1a), 3.94 %1H, d, J3.1 Hz, H-
400), 3.85±3.79 %4H, m, H-200, 300, 6a0, 6a00), 3.77±3.70%3H,
m, H-1b, 6b0, 6b00), 3.64±3.62 %1H, m, H-50), 3.62 %1H, dd,
J11.0, 5.1 Hz, H-3a), 3.60 %1H, dd, J11.0, 3.3 Hz, H-3b),