H. Imai et al. / Tetrahedron 56 (2000) 8451±8459
8457
pyranosyl]-1,2-di-O-12-methyltridecanoyl-sn-glycerol (14).
To a solution of 13 (40.8 mg, 43.3 mmol), DMAP (5.0 mg,
41 mmol), and 12-methyltridecanoic acid (90.2 mg,
395 mmol) in CH2Cl2 was added 1-ethyl-3-(3-dimethyl-
aminopropyl)-carbodiimide hydrochloride (68.8 mg, 359
mmol), and the solution was stirred for 13 h. The reaction
mixture was diluted with ethyl acetate. The mixture was
washed with H2O and brine. The combined organic layers
were dried over MgSO4. Concentration followed by ¯ash
column chromatography gave 14 (59 mg, 37 mmol, 98%) as
colorless viscous oil: [a]2D5.5158.18 (c 1.04, CHCl3); IR
(®lm) n 3066, 3032, 2928, 2858, 1742, 1497, 1456, 1383,
H50), 3.81 (1H, dd, J11.3, 2.3 Hz, H600), 3.82 (1H, dd,
J10.7, 5.4 Hz, H3), 3.84 (1H, ddd, J10.1, 5.5, 2.3 Hz,
H500), 4.20 (1H, dd, J11.8, 4.9 Hz, H1), 4.22 (1H, dd,
J11.7, 4.9 Hz, H60), 4.35 (1H, dd, J11.7, 2.0 Hz, H60),
4.44 (1H, dd, J11.8, 3.3 Hz, H1), 4.93 (1H, d, J3.7 Hz,
H100), 4.97 (1H, d, J3.9 Hz, H10), 5.17±5.23 (1H, m, H2);
13C NMR (125 MHz, CDCl3/CD3OD1/1) d 22.9, 25.5,
28.0, 28.5, 29.7- 30.5, 34.6, 34.7, 34.8, 39.6, 62.2, 63.3,
64.2, 66.5, 70.5, 70.6, 70.9, 71.0, 72.5, 72.7, 73.0, 74.3,
77.2, 97.0, 97.5, 174.2, 174.7, 174.9; MALDI TOF-MS
Calcd for M1Na1 (C57H106O16Na):1069.74. Found:
1069.74. Anal. Calcd for C57H108O17 (M1H2O):C, 64.26;
H, 10.22. Found: C, 64.49; H, 10.36.
1
1365, 1259, 1210, 1160, 1073, 737, 698 cm21; H NMR
(500 MHz, CDCl3) d 0.86 (18H, d, J6.4 Hz, CH(CH3)2),
1.11±1.17 (6H, m), 1.21±1.31 (42H, m), 1.51 (3H, septet,
J6.4 Hz, CH(CH3)2), 1.53±1.64 (6H, m), 2.21±2.32 (6H,
m), 3.40 (1H, dd, J10.8, 1.9 Hz, H600), 3.48 (1H, dd,
J9.9, 8.8 Hz, H40), 3.50 (1H, dd, J10.8, 3.0 Hz, H600),
3.53 (1H, dd, J10.6, 5.0 Hz, H3), 3.59 (1H, dd, J10.3,
3.3 Hz, H200), 3.68 (1H, dd, J10.2, 9.1 Hz, H400), 3.73 (1H,
dd, J10.6, 5.5 Hz, H3), 3.74 (1H, dd, J9.9, 3.2 Hz, H20),
3.84 (1H, dt, J9.9, 3.4 Hz, H50), 3.96 (1H, ddd, J10.2,
3.0, 1.9 Hz, H500), 3.99 (1H, dd, J9.9, 8.8 Hz, H30), 4.04
(1H, dd, J10.1, 9.1 Hz, H300), 4.18 (1H, dd, J11.8,
6.1 Hz, H1), 4.27 (2H, brs, H60£2), 4.31 (1H, d,
J12.5 Hz, Bn), 4.33 (1H, dd, J12.0, 3.4 Hz, H1), 4.43
(1H, d, J10.9 Hz, Bn), 4.53 (1H, d, J10.7 Hz, Bn), 4.53
(1H, d, J12.5 Hz, Bn), 4.72 (1H, d, J11.9 Hz, Bn), 4.75
(1H, d, J11.9 Hz, Bn), 4.80 (1H, d, J11.0 Hz, Bn), 4.81
(1H, d, J10.9 Hz, Bn), 4.82 (1H, d, J11.0 Hz, Bn), 4.86
(1H, d, J10.7 Hz, Bn), 4.94 (1H, d, J10.8 Hz, Bn), 4.95
(1H, d, J3.2 Hz, H10), 4.95 (1H, d, J10.8 Hz, Bn), 5.00
(1H, d, J3.3 Hz, H100), 5.12±5.17 (1H, m, H2), 7.06±7.35
(30H, m, Bn); 13C NMR (125 MHz, CDCl3) d 22.6, 24.9,
24.9, 24.9, 27.4, 28.0, 29.1±29.9, 34.1, 34.1, 34.2, 39.0,
62.6, 62.6, 66.4, 68.0, 69.2, 69.8, 70.5, 72.9, 73.3, 74.8,
75.1, 75.6, 75.9, 76.0, 77.6, 77.8, 79.1, 80.5, 82.1, 95.4,
96.3, 127.4±128.4, 137.8, 137.9, 138.1, 138.2, 138.6, 138.7,
172.9, 173.2, 173.4; MALDI TOF-MS Calcd for M1Na1
(C99H142O16Na):1610.02. Found: 1610.02. Anal. Calcd for
C99H142O16:C,74.87; H, 9.01. Found: C, 75.03; H, 9.08.
3-O-(2-O-a-d-Glucopyranosyl-6-O-tetradecanoyl-a-d-
glucopyranosyl)-1,2-di-O-tetradecanoyl-sn-glycerol (1b).
A colorless waxy solid: [a]2D9152.78 (c 0.12, CHCl3); IR
(®lm) n 3391, 2918, 2850, 1738, 1468, 1377, 1257, 1164,
1054, 721 cm21; 1H NMR (500 MHz, CDCl3/CD3OD1/1)
d 0.85 (9H, t, J7.0 Hz, CH2CH3), 1.21±1.32 (60H, m),
1.55±1.62 (6H, m, COCH2CH2), 2,28±2.33 (6H, m,
COCH2), 3,29 (1H, dd, J9.9, 9.1 Hz, H400), 3.30 (1H, dd,
J9.9, 9.1 Hz, H40), 3.39 (1H, dd, J9.7, 3.9 Hz, H200),
3.56 (1H, dd, J9.8, 3.6 Hz, H20), 3.62 (1H, dd, J10.8,
5.0 Hz, H3), 3.66 (1H, dd, J11.9, 5.5 Hz, H600), 3.66 (1H,
dd, J9.7, 9.1 Hz, H300), 3.73 (1H, dd, J9.8, 9.1 Hz, H30),
3.74 (1H, ddd, J9.9, 6.3, 2.1 Hz, H50), 3.81 (1H, dd,
J10.8, 5.5 Hz, H3), 3.81 (1H, dd, J11.9, 2.5 Hz, H600),
3.84 (1H, ddd, J9.9, 5.5, 2.5 Hz, H500), 4.20 (1H, dd,
J12.1, 6.2 Hz, H1), 4.21 (1H, dd, J11.8, 6.3 Hz, H60),
4.34 (1H, dd, J11.8, 2.1 Hz, H60), 4.43 (1H, dd, J12.1,
3.2 Hz, H1), 4.92 (1H, d, J3.9 Hz, H100), 4.95 (1H, d,
J3.6 Hz, H10), 5.18±5.22 (1H, m, H2); 13C NMR
(125 MHz, CDCl3/CD3OD1/1) d 14.3, 23.1, 25.4, 25.4,
25.4, 25.6, 25.6, 29.6, 29.6, 29.8, 29.8, 30.0, 30.1, 30.1,
32.4, 34.6, 34.6, 34.7, 62.1, 63.2, 64.0, 66.4, 70.4, 70.5,
70.7, 70.9, 72.4, 72.6, 72.9, 74.2, 77.2, 97.0, 97.4, 174.1,
174.6, 174.9; MALDI TOF-MS Calcd for M1Na1
(C57H106O16Na):1069.74. Found: 1069.74.
3-O-(2-O-a-d-Glucopyranosyl-6-O-hexadecanoyl-a-d-
glucopyranosyl)-1,2-di-O-hexadecanoyl-sn-glycerol (1c).
A colorless waxy solid: [a]2D8146.68 (c 0.12, CHCl3); IR
(®lm) n 3388, 2918, 2850, 1739, 1467, 1163, 1055, 759,
721 cm21; 1H NMR (500 MHz, CDCl3/CD3OD1/1) d 0.84
(9H, t, J6.8 Hz, CH2CH3), 1.18±1.31 (72H, m), 1.54±1.63
(6H, m, COCH2CH2), 2.28±2.33 (6H, m, COCH2), 3.28±
3.33 (2H, m, H40, H400), 3.37 (1H, dd, J9.6, 3.8 Hz, H200),
3.56 (1H, dd, J9.7, 3.5 Hz, H20), 3.59 (1H, dd, J10.5,
5.2 Hz, H3), 3.65 (1H, dd, J9.6, 9.1 Hz, H300), 3.66 (1H,
dd, J12.3, 5.2 Hz, H600), 3.73 (1H, t, J9.4 Hz, H30),
3.72±3.77 (1H, m, H50), 3.80 (1H, dd, J10.5, 5.2 Hz,
H3), 3.81 (1H, dd, J12.3, 2.5 Hz, H600), 3.81±3.85 (1H,
m, H500), 4.19 (1H, dd, J12.2, 6.1 Hz, H1), 4.21 (1H, dd,
J12.2. 6.1 Hz, H60), 4.33 (1H, dd, J12.2, 2.0 Hz, H60),
4.42 (1H, dd, J12.3, 3.3 Hz, H1), 4.91 (1H, d, J3.8 Hz,
H100), 4.95 (1H, d, J3.5 Hz, H10), 5.17±5.22 (1H, m, H2);
13C NMR (125 MHz, CDCl3/CD3OD1/1) d 14.3, 23.2,
25.5, 25.5, 25.6, 29.7, 29.8, 29.9, 30.0, 30.1, 30.3, 30.3,
32.5, 34.7, 34.7, 34.8, 62.2, 63.4, 64.3, 66.5, 70.6, 70.7,
71.0 (2£C), 72.6, 72.8, 73.0, 74.4, 77.2, 97.1, 97.5, 174.2,
174.7, 175.0; MALDI TOF-MS Calcd for M1Na1
(C63H118O16Na): 1153.83. Found: 1153.84.
3-O-(2-O-a-d-Glucopyranosyl-6-O-12-methyltrideca-
noyl-a-d-glucopyranosyl)-1,2-di-O-12-methyltrideca-
noyl-sn-glycerol (1a). A solution of 14 (498 mg, 314 mmol)
in ethyl acetate (6 mL) and ethanol (1.2 mL) was treated
with 5% palladium on charcoal (360 mg) and stirred at
ambient temperature under hydrogen atmosphere for 8 h.
The catalyst was ®ltered off through a plug of Celitew,
and the solvent was removed in vacuo. The residue was
puri®ed by ¯ash column chromatography to afford 1a
(250 mg, 238 mmol, 76%) as a colorless waxy solid:
[a]2D6166.38 (c 0.11, CHCl3); IR (®lm) n 3386, 2924,
2856, 1742, 1466, 1367, 1162, 1058, 919, 762, 725 cm21
;
1H NMR (500 MHz, CDCl3/CD3OD1/1) d 0.84 (18H, d,
J6.6 Hz, CH(CH3)2), 1.10±1.16 (6H, m, CH2CH(CH3)2),
1.22±1.33 (42H, m), 1.49 (3H, septet, J6.6 Hz,
CH(CH3)2), 1.55±1.63 (6H, m, COCH2CH2), 2.27±2.34
(6H, m, COCH2), 3.27±3.33 (2H, m, H40, H400), 3.39 (1H,
dd, J9.3, 3.9 Hz, H200), 3.57 (1H, dd, J9.9, 3.7 Hz, H20),
3.63 (1H, dd, J10.7, 5.0 Hz, H3), 3.66 (1H, dd, J11.3,
5.5 Hz, H600), 3.67 (1H, dd, J9.4, 9.3 Hz, H300), 3.74 (1H,
dd, J9.9, 8.6 Hz, H30), 3.76 (1H, ddd, J9.4, 4.9, 2.0 Hz,