10
G. Milkereit et al. / Chemistry and Physics of Lipids 135 (2005) 1–14
4.74 (dd, 1H, H-2ꢀ), 4.70 (d, 1H, H-1ꢀ), 4.40 (dd,
1H, H-6aꢀ), 4.19 (dd, 1H, H-6aꢀꢀ), 4.15 (dd, 1H,
H-6bꢀ), 3.97 (dd, 1H, H-6bꢀꢀ), 3.91 (t, 1H, H-4ꢀ),
3.80–3.91 (m, 2H, H-2, H-5ꢀꢀ), 3.59 (ddd, 1H, H-5ꢀ),
3.44–3.51 (m, 2H, H-1a, H-3a), 3.29–3.38 (m, 6H,
H-1b, H-3b, alkyl-␣-CH2), 2.07, 2.03, 1.98, 1.96
(each s, 3H, OAc), 1.93 (s, 6H, OAc), 1.92 (s,
3H, OAc), 1.42–1.52 (m, 4H, -CH2), 1.16–1.25
(m, 44H, alkyl-CH2), 0.81 (t, 6H, alkyl-CH3);
3
3
3
3
2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J4 ,5 = 9.1, J5 ,6a = 2.1, J5 ,6b = 5.7, J6a ,b = 12.1,
ꢀꢀ ꢀꢀ
J1 ,2 = 3.6 Hz.
4.2.8. 1,3-Di-O-[(2ꢀR,4ꢀR,6ꢀR,8ꢀR)-2ꢀ,4ꢀ,6ꢀ,8ꢀ-
tetramethyldecyl]-2-O-[4ꢀꢀ-O-(2ꢀꢀꢀ,3ꢀꢀꢀ,4ꢀꢀꢀ,6ꢀꢀꢀ-
tetra-O-acetyl-α-d-glucopyranosyl)-2ꢀꢀ,3ꢀꢀ,4ꢀꢀ-tri-
O-acetyl-β-d-glucopyranosyl]-sn-glycerol (19)
The reaction was carried out as described for
17 using 1.83 g (2.7 mmol) Maltoseperacetate, 1.3 g
(2.7 mmol) 3 and 537 mg (475 L; 3.78 mmol) boron
trifluoride etherate. The product was purified using
light petroleum b.p. 50–70 ◦C–ethyl acetate 2:1 as elu-
ent.
3
3
3
3
3
3
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
J1 ,2 = 8.1, J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7,
3
2
3
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
J5 ,6a = 2.8, J5 ,6b = 4.8, J6a ,6b = 12.2, J1 ,2 = 3.8,
3
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ
J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7, J5 ,6a = 4.1,
2
J5 ,6b = 2.3,
J6a ,6b = 12.9,
3JCH ,CH
=
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
2 3
Yield: 1.04 g (35%). C57H98O20 (1102.6651)
6.6 Hz.
1H NMR (500 MHz, CDCl3 + TMS): δ = 5.36 (d,
1H, H-1ꢀꢀꢀ), 5.28 (dd, 1H, H-3ꢀꢀꢀ), 5.21 (dd, 1H, H-3ꢀꢀ),
5.00 (t, 1H, H-4ꢀꢀꢀ), 4.85 (dd, 1H, H-2ꢀꢀꢀ), 4.76 (dd, 1H,
H-2ꢀꢀ), 4.74 (d, 1H, H-1ꢀꢀ), 4.41 (dd, 1H, H-6aꢀꢀ), 4.19
(dd, 1H, H-6aꢀꢀꢀ), 4.14 (dd, 1H, H-6bꢀꢀ), 3.96 (dd, 1H,
H-6bꢀꢀꢀ), 3.92 (t, 1H, H-4ꢀꢀ), 3.81–3.95 (m, 2H, H-2,
H-5ꢀꢀꢀ), 3.61 (ddd, 1H, H-5ꢀꢀ), 3.44–3.50 (m, 2H, H-1a,
H-3a), 3.28–3.40 (m, 6H, H-1b, H-3b, H-1aꢀ, H-1bꢀ),
2.56 (m, 2H, H-2ꢀ), 2.07, 2.03, 1.98, 1.96 (each s, 3H,
OAc), 1.94 (s, 6H, OAc), 1.91 (s, 3H, OAc), 1.78 (m,
2H, H-3aꢀ), 1.52–1.70 (m, 4H, H-4ꢀ, H-6ꢀ), 1.28–1.50
(m, 4H, H-8ꢀ, H-9aꢀ), 1.16–1.26 (m, 10H, H-5aꢀ, H-7aꢀ,
CH3-2ꢀ), 0.98–1.13 (m, 4H, H-3bꢀ, H-9bꢀ), 0.79–0.95
(m, 4H, H-5bꢀ, H-7bꢀ), 0.90 (d, 6H, CH3-4ꢀ), 0.85 (t,
6H, CH3-10ꢀ), 0.83 (m, 6H, CH3-8ꢀ), 0.79 (d, 6H, CH3-
13C NMR (100 MHz, CDCl3 + TMS): δ = 170.94,
170.87, 170.62, 170.34, 170.05, 169.82 (C=O, OAC),
100.66 (C-1ꢀꢀ), 95.94 (C-1ꢀ), 78.75 (C-2), 75.94
(C-3ꢀ), 73.25 (C-4ꢀ), 72.81 (C-2ꢀ), 72.43 (C-5ꢀ),
72.19, 72.10 (C-␣), 71.66, 70.92 (C-1, C-3), 70.40
(C-2ꢀꢀ), 70.09 (C-3ꢀꢀ), 69.80 (C-5ꢀꢀ), 68.47 (C-4ꢀꢀ),
63.33 (C-6ꢀ), 61.94 (C-6ꢀꢀ), 32.34, 30.12, 30.08,
29.95, 29.78, 26.56, 26.53, 23.11 (alkyl-CH2), 21.35,
21.25, 21.11, 21.06, 21.00 ( CH3, OAc), 14.54
(alkyl-CH3).
4.2.7. 1,3-Di-O-tetradecyl-2-O-[4ꢀ-O-(α-d-
glucopyranosyl)-β-d-glucopyranosyl]-sn-
glycerol (18)
2.98 g (2.70 mmol) 17 were deprotected using gen-
eral procedure 1. The product was recrystallised from
methanol.
3
3
3
3
6ꢀ).ꢀ J1 ,2 = 8.1, ꢀ J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7,
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
3J5
= 2.8, 3J5
= 4.8, J6a ,6b = 12.2, J1 ,2 = 3.8,
2
3
,6aꢀ
,6bꢀ
ꢀꢀ ꢀꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
3
3
3
3
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
ꢀꢀ
ꢀꢀ
J2 ,3 = 9.7, J3 ,4 = 9.7, J4 ,5 = 9.7, J5 ,6a = 4.1,
Yield: 2.10 g (90%). C43H84O13 (808.5912).
3
2
ꢀꢀ
ꢀꢀ
ꢀꢀ
ꢀꢀ
J5 ,6b = 2.3, J6a ,6b = 12.9 Hz.
MALDITOF-MS: m/z = 831.6 [M + Na]+
13C NMR (100 MHz, CDCl3 + TMS): δ = 170.98,
Calc.
C 63.83
H 10.46
Found
C 63.92
H 10.58
170.90, 170.68, 170.34, 170.12, 169.92 (C=O, OAC),
100.54 (C-1ꢀꢀꢀ), 95.98 (C-1ꢀꢀ), 78.76 (C-2), 75.92 (C-
3ꢀꢀ), 73.26 (C-4ꢀꢀ), 72.81 (C-2ꢀꢀ), 72.43 (C-5ꢀꢀ), 72.25,
72.14 (C-1aꢀ, C-1bꢀ), 71.98, 71.05 (C-1, C-3), 70.48
(C-2ꢀꢀꢀ), 70.25 (C-3ꢀꢀꢀ), 69.78 (C-5ꢀꢀꢀ), 68.55 (C-4ꢀꢀꢀ),
63.42 (C-6ꢀꢀ), 61.98 (C-6ꢀꢀꢀ), 45.48, 44.87, 44.84 (C-
5aꢀ, C-5bꢀ, C-7aꢀ, C-7bꢀ), 41.51, 41.34 (C-3aꢀ, C-
3bꢀ), 31.57 (C-8aꢀ, C-8bꢀ), 31.07, 30.86 (C-2aꢀ, C-2bꢀ),
28.93, 28.89 (C-9aꢀ, C-9bꢀ), 28.07, 28.03 (C-4aꢀ, C-
4bꢀ), 27.26, 27.24 (C-6aꢀ, C-6bꢀ), 21.69, 21.65, 21.64,
21.59, 21.48, 21.45 (CH3-4aꢀ, CH3-4bꢀ, CH3-6aꢀ, CH3-
6bꢀ, CH3-8aꢀ, CH3-8bꢀ), 21.36, 21.26, 21.12, 21.07,
21.01 ( CH3, OAc), 18.98 (CH3-2aꢀ, CH3-2bꢀ), 11.25
(CH3-10aꢀ, CH3-10bꢀ).
[α]2D0 = +20◦ (c = 1.0, MeOH)
1H NMR (500 MHz, d4-Methanol): δ = 5.19 (d,
1H, H-1ꢀꢀ), 4.30 (d, 1H, H-1ꢀ), 3.94–3.96 (m, 1H,
H-2), 3.89 (dd, 1H, H-6aꢀ), 3.76–3.87 (m, 3H, H-
4ꢀꢀ, H-6bꢀ, H-6aꢀꢀ), 3.66–3.73 (m, 2H, H-5ꢀꢀ, H-
6bꢀꢀ), 3.58–3.63 (m, 2H, H-3ꢀ, H-3ꢀꢀ), 3.52 (dd, 1H,
H-4ꢀ), 3.43–3.50 (m, 3H, H-1a, H-3a, H-2ꢀꢀ), 3.39
(ddd, 1H, H-5ꢀ), 3.22–3.29 (m, 3H, H-1b, H-3b,
H-2ꢀ), 3.17–3.21 (m, 4H, alkyl-␣-CH2), 1.41–1.50
(m, 4H, alkyl--CH2), 1.16–1.35 (m, 44H, alkyl-
CH2), 0.88 (t, 6H, alkyl-CH3); 3J1 ,2 = 8.1, J3 ,4 = 9.1,
3
ꢀ
ꢀ
ꢀ
ꢀ