U. Eichelberger et al. / Tetrahedron 58 (2002) 545±559
551
(1)176.65 (C-1). C25H45NO4 (423.63, 423.33). FAB MS:44
m/z424.4 [M1H]1, 130.1; HRMS: calcd 424.3427, found
424.3421.
1436, 1359, 1249, 1197, 1172, 1110, 972, 860, 838,
1
695 cm21. H NMR (200 MHz, CDCl3): d0.00 (s, 9H,
Si(CH3)3), 0.82±0.96 (m, 5H, CH3-18, CH2±CH2±Si),
1.21±1.38 (m, 20H, CH2-4±CH2-7, CH2-12±CH2-17),
1.40±1.65 (m, 2H, CH2-3), 1.92±2.12 (m, 4H, CH2-8,
CH2-11), 2.58±2.74 (m, 1H, 2-H), 3.38±3.63 (m, 4H,
O±CH2±CH2±Si, CH±CH2±OH), 3.69 (s, 3H, OCH3),
5.31±5.39 (m, 2H, 9-H, 10-H). 13C NMR (50.3 MHz,
CDCl3): d21.23 (Si(CH3)3), 14.27 (CH3-18), 18.12
(CH2±CH2±Si), 22.84, 27.31, 27.38, 29.21, 29.47, 29.56,
29.68, 29.81, 29.92, 32.06 (C-3±C-7, C-8±C-17), 46.37
(C-2), 51.68 (OCH3), 68.49 (CH2±CH2±Si), 71.29 (CH±
CH2±O), 129.86, 130.13 (C-9, C-10), 175.48 (C-1).
C25H50O3Si (426.76, 426.15), FAB MS: m/z427.1
[M1H]1.
8.6.3. (S)-3-[(R)-2-Acetoxymethyl-oleoyl]-4-isopropyl-
oxazolidin-2-one (formula not shown). General procedure
2: 9A (0.20 g, 0.50 mmol), 8a (0.10 g, 1 mmol), FC
(petroleum ether±ethyl acetate 3:1). Colourless oil, yield:
24
0.14 g (59%). [a]D 124.2 (c0.94, CHCl3). IR (KBr):
3420, 2854, 2798, 1786, 1747, 1703, 1461, 1379,
1
1227 cm21. H NMR (200 MHz, CDCl3): d0.87, 0.91
(2d, 6H, CH(CH3)2aux, J7.2 Hz), 0.86±0.98 (m, 3H,
CH3-18), 1.12±1.41 (m, 20H, CH2-4±CH2-7, CH2-12±
CH2-17), 1.42±1.80 (m, 2H, CH2-3), 1.85±2.10 (m, 4H,
CH2-8, CH2-11), 2.11 (s, 3H, CH3COO), 2.23±2.41 (m,
1H, CH(CH3)2aux), 4.02±4.36 (m, 5H, 2-H, CH±CH2±O,
CH2-5aux), 4.45 (ddd, 1H, 4aux-H), 5.24±5.41 (m, 2H, 9-H,
10-H). 13C NMR (50.3 MHz, CDCl3): d14.48 (CH3-18),
15.09, 18.35 (CH(CH3)2aux), 21.10 (CH3COO), 28.89
(CH(CH3)2aux), 23.06, 27.11, 27.53, 27.60, 29.44, 29.71,
29.90, 30.01, 30.15, 32.29 (C-3±C-8, C-11±C-17), 42.80
(C-2), 59.00 (C-4aux), 63.73 (CH±CH2±O), 64.68 (C-5aux),
130.17, 130.54 (C-9, C-10), 154.31 (C-2aux), 171.30
(CH3COO), 174.55 (C-1). C27H47NO5 (465.67, 465.35). EI
MS: m/z (%)465 [M]1z (7), 405 (30), 276 (29), 130 (75),
55 (51), 43 (100), 41 (37); HRMS: calcd 465.3454, found
465.3488
8.6.6. Methyl (R)-2-hydroxymethyl oleate (11Aa). (a)
General procedure 5: 11Ab (0.45 g, 1.05 mmol), LiBF4
(0.49 g, 5.25 mmol), 98:2 CH3CN±water (10 mL), FC
(petroleum ether±ethyl acetate 3:1), yield: 0.25 g (72%).
(b) General procedure 4: 10Aa (88.60 mg, 0.22 mmol),
,
magnesium methoxide (0.1 mol L21
(petroleum ether±ethyl acetate 3:1), yield 68 mg (93%).
4.6 mL), FC
24
[a]D 17.7 (c2.07, CHCl3). CD: lmax (De)212.8 nm
(2.05). IR (KBr): 3411, 2925, 2855, 1739, 1462, 1439, 1199,
1170, 1049 cm21. 1H NMR (200 MHz, CDCl3): d0.87 (t,
3H, CH3-18, J6.5 Hz), 1.18±1.39 (20H, CH2-4±CH2-7,
CH2-12±CH2-17), 1.42±1.70 (2H, CH2-3), 1.89±2.08 (4H,
CH2-8, CH2-11), 2.24 (bs, 1H, OH), 2.43±2.53 (1H, 2-H),
3.71 (s, 3H, OCH3), 3.71±3.80 (2H, CH2±OH), 5.24±5.41
(2H, 9-H, 10-H). 13C NMR (APT, 50.3 MHz, CDCl3):
d(2)14.47 (CH3-18), (1)23.06, (1)27.52, (1)27.60,
(1)28.87, (1)29.43, (1)29.70, (1)29.81, (1)29.91,
(1)30.04, (1)30.15, (1)32.29 (C-3±C-8, C-11±C-17),
(2)47.89 (C-2), (2)52.12 (OCH3), (1)63.57 (CH2±OH),
(2)130.19, (2)130.54 (C-9, C-10), (1)176.50 (C-1).
C20H38O3 (326.51, 326.28), EI MS: m/z (%)326 [M]1z
(7), 308 (7), 245 (15), 104 (90), 55 (100), 43 (62), 41
(79); HRMS: calcd 326.2821, found 326.2832
8.6.4.
oleoyl]-4-isopropyloxazolidin-2-one (10Ab). General
procedure 2: 9A (0.97 g, 2.46 mmol), (0.61 g,
(S)-3-[(R)-2-(2-Trimethylsilyl-ethoxymethyl)-
7
3.70 mmol), FC (petroleum ether±ethyl acetate 5:1).
24
Colourless oil, yield: 1.06 g (84%). [a]D 120.9
(c7.16, CHCl3). IR (KBr): 2926, 2854, 1782, 1703,
1
1464, 1387, 1365, 1302, 1248, 1101, 860, 837 cm21. H
NMR (200 MHz, CDCl3): d20.01 (s, 9H, Si(CH3)3),
0.87 (2t, 6H, CH2±CH2±Si, CH3-18, J8.2 Hz), 0.88,
0.91 (2d, 6H, CH(CH3)2aux, J5.9 Hz), 1.18±1.37 (m,
20H, CH2-4±CH2-7, CH2-12±CH2-17), 1.44±1.78 (m, 2H,
CH2-3), 1.90±2.12 (m, 4H, CH2-8, CH2-11), 2.28±2.46 (m,
1H, CH(CH3)2aux), 3.41±3.52 (m, 2H, CH2±CH2±Si), 3.54
2
3
(dd, 1H, CH±CHH0 ±O, J9.2 Hz, J5.1 Hz), 3.64 (dd,
1H, CH±CHH0 ±O, 3J7.7 Hz), 4.08±4.19 (m, 1H,
CH±CH2±O), 4.18 (dd, 1H, 5aux-H, 2J9.2 Hz,
8.6.7. (4R,5S)-3-Oleoyl-4-methyl-5-phenyl-oxazolidin-2-
one (12). General procedure 1: (4R,5S)-4-methyl-5-phenyl-
oxazolidin-2-one (6, 0.18 g, 1.0 mmol), oleoyl chloride
(0.30 g, 1.0 mmol), FC (petroleum ether±ethyl acetate 5:1).
3
3J3.7 Hz), 4.26 (dd, 1H, 5aux-H0, J8.1 Hz), 4.50 (ddd,
1H, 4aux-H), 5.28±5.39 (m, 2H, 9-H, 10-H). 13C NMR
(HETCOR, APT, 50.3 MHz, CDCl3): d(2)1.26
(Si(CH3)3), (2)14.27 (CH3-18), (2)14.86, (2)18.05
(CH(CH3)2aux), (1)18.21 (CH2±CH2±Si), (2)28.49
(CH(CH3)2), (1)22.84, (1)27.37, (1)29.09, (1)29.25,
(1)29.47, (1)29.67, (1)29.74, (1)29.81, (1)29.92,
(1)32.05 (C-3±C-8, C-11±C-17), (2)43.69 (CH±CH2±
O), (2)58.64 (C-4aux), (1)63.19 (C-5aux), (1)68.44 (CH2±
CH2±Si), (1)71.77 (CH±CH2±O), (2)129.88, (2)130.08
(C-9, C-10), (1)153.90 (C-2aux), (1)175.42 (C-1).
C29H55NO4Si (509.85, 509.39), ESI MS: m/z1069.79929,
calcd for C58H110N2NaO8Si2 [2M1Na]1: 1069.80059.
Colourless oil, yield: 0.34 g (76%). [a]D 251.4 (c2.56,
24
CHCl3). IR (KBr): 3385, 2927, 2856, 1785, 1703, 1456,
1
1348, 1246, 1199, 1150, 1122, 768, 701 cm21. H NMR
(200 MHz, CDCl3): d0.88 (t, 3H, CH3-18), 0.90 (d, 3H,
aux
4-CH3
,
J6.6 Hz), 1.18±1.43 (20H, CH2-4±CH2-7,
CH2-12±CH2-17), 1.57±1.78 (2H, CH2-3), 1.91±2.10 (4H,
CH2-8, CH2-11), 2.80±3.08 (2H, CH2-2), 4.77 (dq, 1H,
4
aux-H, J4,57.0 Hz), 5.31±5.39 (2H, 9-H, 10-H), 5.66 (d,
1H, 5aux-H), 7.26±7.48 (5H, Harom). 13C NMR (50.3 MHz,
CDCl3): d14.59 (CH3-18), 15.05 (4-CH3aux), 23.16, 24.79,
27.70, 29.47, 29.62, 29.80, 30.00, 30.09, 30.20, 30.26,
32.39 (C-3±C-8, C-11±C-17), 36.12 (C-2), 55.22 (C-4aux),
79.43 (C-5aux), 126.13, 129.18, 129.20, 133.89 (6£Carom),
130.26, 130.46 (C-9, C-10), 153.53 (C-2aux), 173.66
(C-1). C28H43NO3 (441.65, 441.32), EI MS: m/z (%)441
[M]1z (17), 232 (32), 219 (56), 178 (45), 159 (31), 134
(75), 55 (100), 43 (95); HRMS: calcd 441.3243, found
441.3243.
8.6.5. Methyl (2R)-2-(2-trimethylsilyl-ethoxymethyl)-
oleate (11Ab). General procedure 4: 10Ab (0.74 g,
1.45 mmol), FC (petroleum ether±ethyl acetate 10:1).
24
Colourless oil, yield 0.47 g (75%). [a]D 111.4
(c0.85, CHCl3). IR (KBr): 2927, 2856, 1742, 1653,