1689
Derivatives of chiral oxazolidin-2-ones
128.5 (CH), 130.9 (CH), 133.3 (CH), 151.9 (C), 153.9 (C); MS (CI~H4): 324 ([M+I]÷, 100%),
352 ([M+29]+, 28%), 364 ([M+41] ÷, 12%); Anal. calcd, for C2oH21NO3: C, 74.28%; H, 6.55%; N,
4.33%. Found: C, 74.03%; H, 6.56%; N, 4.24%.
(1R,5S, 7S)-1-(10, lO-Dimethyl-3,3-dioxo-3-thia-4-azatricyclo[5.2.1.0 l'5]dec-4-yl)-3-phenyl-2-
propyn- l-one 2d
Prepared by the general procedure from ld (0.22 g, 1.00 mmol) in 92% yield (0.32 g). White solid.
mp 148-150°C; [cX]25D=+47.6 (c=0.8, CHCI3); IR (KBr): 3020, 3000, 29060, 2880, 2230, 1660,
1490, 1450, 1375, 1330, 1300, 1225, 1180, 1140, 770, 730, 695 cm-l; lH-NMR (200 MHz): 0.99
(s, 3H), 1.21 (s, 3H), 1.30-1.50 (m, 2H), 1.91-2.40 (m, 5H), 3.40-3.60 (m, 2H), 3.90--4.01 (t, J=5.5
Hz, 1H), 7.33-7.45 (m, 3H), 7.63-7.67 (m, 2H); 13C-NMR (50 MHz): 19.8 (CH3), 20.8 (CH3), 26.3
(CH2), 32.7 (CH2), 38.3 (CH2), 44.7 (CH), 47.7 (C), 48.4 (C), 52.9 (CH2), 64.9 (CH), 80.9 (C), 92.2
(C), 119.4 (C), 128.5 (CH), 130.9 (CH), 133.1 (CH), 150.0 (C); MS (CI-NH3): 344 ([M+I]+, 56%),
361 ([M+18]÷, 100%); Anal. calcd, for C19H21NO3S: C, 66.45%; H, 6.16%; N, 4.08%; S, 9.33%.
Found: C, 66.15%; H, 6.30%; N, 3.78%; S=8.89%.
(4S )-3-( 2-Butynoyl )-4-benzyloxazolidin-2-one 3a
Prepared by the general procedure from la (0.63 g, 3.57 mmol) in 88% yield (0.76 g). White solid.
mp 78-80°C; [Ot]25D=+60.4 (c=0.84, CHCI3); IR (KBr): 3060, 3020, 2960, 2910, 2220, 2210, 1795,
1650, 1350, 1320, 1210, 1090, 755,730, 700 cm-1; 1H-NMR (200 MHz): 2.11 (s, 3H), 2.74-2.86 (dd,
J=13.5 Hz, J'=9.5 Hz, 1H), 3.25-3.33 (dd, J=13.5 Hz, J'=3.3 Hz, IH), 4.15-4.19 (m, 2H), 4.60--4.74
(m, IH), 7.19-7.34 (m, 5H); 13C-NMR (50 MHz): 4.4 (CH3), 37.4 (CH2), 54.9 (CH), 65.8 (CH2), 72.7
(C), 94.7 (C), 127.3 (CH), 129.0 (CH), 129.2 (CH), 134.8 (C), 151.0 (C), 153.0 (C); MS (CI-NH3):
244 ([M+I]+, 5%), 261 ([M+18]+, 100%); Anal. caicd, for Cj4HI3NO3: C, 69.14%; H, 5.35%; N,
5.76%. Found: C, 69.14%; H, 5.38%; N, 5.75%.
(4S )-3-( 2-Butynoyl)-4-phenyloxazolidin-2-one 3b
Prepared by the general procedure from lb (0.91 g, 2.50 mmol) in 87% yield (0.50 g). Colorless oil.
[0~]25D=+7.97 (c=4.5, CHC13); IR (film NaCI): 3060, 3040, 2980, 2930, 2240, 2220, 1795, 1670,1390,
1330, 1200, 1190, 910, 760, 720, 700 cm-I; IH-NMR (200 MHz): 2.17 (s, 3H), 4.20--4.30 (dd, J=9
Hz, J'=4.5 Hz, IH), 4.60--4.71 (m, 1H), 5.35-5.45 (dd, J=9 Hz, J'=4.5 Hz, IH), 7.20-7.40 (m, 5H);
13C-NMR (50 MHz): 4.5 (CH3), 57.5 (CH), 69.5 (CH2), 72.8 (C), 94.8 (C), 126.0 (CH), 128.7 (CH),
129.2 (CH), 138.5 (C), 150.0 (C), 152.0 (C); MS (CI-NH3): 230 ([M+I]+, 6%), 247 ([M+18]+, 100%).
(1S,2R,6S, 7R)- 7,10,10- Trimethyl-5-( 2- butynoyl)- 3-oxa-5-azatricyclo[ 5.2.1.02' 6]decan-4-one 3c
Prepared by the general procedure from lc (0.20 g, 1.03 mmol) in 79% yield (0.21g). White solid.
mp 130-132°C; [0t]25D=+27.2 (c=3.2, CHC13), IR (KBr): 2960, 2920, 2890, 2230, 1785, 1660, 1330,
1105, 1100, 1055, 1045, 990, 950, 800, 765 cm-l; IH-NMR (200 MHz): 0.96 (s, 3H), 0.98 (s,
3H), 1.01 (s, 3H), 0.90-1.15 (m, IH), 1.18-1.34 (m, 1H), 1.47-1.65 (td, J=12.3 Hz, J'=4.6 Hz, 1H),
1.74-1.92 (m, 1H), 2.11 (s, 3H), 2.17-2.19 (d, J=4.8 Hz, 1H), 4.34-4.38 (d, J=7.9 Hz, 1H), 4.50-4.54
(d, J=7.8 Hz, 1H); 13C-NMR (50 MHz): 4.6 (CH3), 11.9 (CH3), 19.7 (CH3), 22.7 (CH3), 22.7 (CH2),
33.2 (CH2), 46.5 (C), 47.5 (CH), 50.2 (C), 65.8 (CH), 72.9 (C), 81.4 (CH), 95.0 (C), 151.5 (C), 153.5
(C); MS (CI-CH4): 262 ([M+I]+, 100%), 290 ([M+29]+, 25%), 302 ([M+41]÷, 11%); Anal. calcd.
for CI5H19NO3: C, 68.95%; H, 7.33%; N, 5.36%. Found: C, 68.85%; H, 7.37%; N, 5.26%.
(1R,5S, 7S)-1- (10,10-Dimethyl- 3, 3-dioxo-3 -thia -4-azatricyclo[5.2.1.01' 5]dec-4-yl)-2- bu tyn- 1-one 3d
Prepared by the general procedure from ld (0.22 g, 1.00 mmol) in 56% yield (0.16 g). White solid.
mp 170-172°C; [0~]25D=+108.4 (c=2, CHC13); IR (KBr): 2990, 2960, 2930, 2240, 1650, 1410, 1340,
1320, 1310, 1285, 1250, 1170, 1140, 1050, 1000, 730 cm-l; IH-NMR (200 MHz): 0.98 (s, 3H), 1.18