W. B. Motherwell et al.
FULL PAPER
mixture of 37a, 37b, 37c and 37d, contaminated by traces of N-
formyl-4,5-diphenyl-2-oxazolidinone, white solid; Fraction 2: 37a,
white solid; 37a: m.p. 181–183 °C (EtOAc/hexane). [α]2D2 = +135.0
91 (11). HMRS: [M + H], found 570.23942. C30H44NO2Sn calcd.
570.23885.
(4R,5S)-3-[(1S,2S)-2-(Benzyldimethylsilanyl)cyclopropyl]-4,5-di-
phenyl-2-oxazolidinone (40): White solid; m.p. 149–151 °C (EtOAc).
(c = 0.9, CHCl ). IR (film): ν
= 3035 (w), 3000 (w), 2920 (w),
˜
3
max
1738 (s), 1604 (w), 1499 (w), 1455 (m), 1403 (s), 1227 (m), 1194
[α]1D8 = +84.5 (c = 1.06, CHCl ). IR (film): ν
= 3025 (w), 2921
˜
(m), 1137 (w), 1134 (m) 1025 (s) cm–1 1H NMR (300 MHz,
.
3
max
(w), 1735 (s), 1452 (m), 1405 (m), 1247 (w), 1247 (m), 1028 (w),
CDCl3): 37a: δ = 1.37 (dt, J = 7.4, 6.6 Hz, 1 H, CHHCHN), 1.37
(ddd, J = 10.0, 6.1, 4.2 Hz, 1 H, CHHCHN), 2.22 (ddd, J = 10.0,
6.6, 3.3 Hz, 1 H, CHCHN), 2.63 (dt, J = 7.4, 3.9 Hz, 1 H, CHN),
5.04 (d, J = 8.0 Hz, 1 H, CHNCO), 5.83 (d, J = 8.0 Hz, 1 H,
CHOCO), 6.80–7.15 (m, 15 H, Ar-H); 37b: δ = 1.05–1.29 (m, 2 H,
CH2CHN), 2.40–2.57 (m, 2 H, CHN and CHCHN), 4.94 (d, J =
7.9 Hz, 1 H, CHNCO), 5.81 (d, J = 7.9 Hz, 1 H, CHOCO), 6.72–
7.44 (m, 15 H, Ar-H); 37c: δ = 1.53 (dt, J = 9.0, 7.2 Hz, 1 H,
CHHCHN), 1.96 (td, J = 7.2, 4.3 Hz, 1 H, CHHCHN), 2.15 (dt,
J = 9.0, 7.2 Hz, 1 H, CHCHN), 2.60 (td, J = 7.2, 4.3 Hz, 1 H,
CHN), 3.80 (d, J = 7.8 Hz, 1 H, CHNCO), 5.15 (d, J = 7.8 Hz, 1
H, CHOCO), 6.71–7.45 (m, 15 H, Ar-H); 37d: δ = 1.05–1.15 (m, 2
H, CH2CHN), 2.44 (dt, J = 8.8, 7.1 Hz, 1 H, CHCHN), 3.09 (ddd,
J = 7.7, 7.1, 4.8 Hz, 1 H, CHN), 4.51 (d, J = 7.7 Hz, 1 H,
CHNCO), 5.32 (d, J = 7.7 Hz, 1 H, CHOCO), 6.71–7.45 (m, 15
H, Ar-H) ppm. 13C NMR (75 MHz, CDCl3): 37a: δ = 15.9, 23.4,
33.9, 66.7, 79.7, 126.0, 126.3, 126.8, 127.6, 127.9, 128.1, 128.2,
128.4, 134.3, 134.4, 139.4, 157.9; 37b: δ = 13.5, 24.9, 34.4, 66.4,
79.7, 126.3, 127.0, 127.4, 127.8, 127.9, 128.3, 129.0, 134.4, 134.6,
139.4, 158.6; 37c: δ = 11.7, 22.5, 31.5, 65.4, 79.6, 125.8, 126.7,
127.6, 128.2, 128.3, 128.4, 133.8, 134.0, 136.5, 158.7; 37d: δ = 9.9,
23.7, 31.7, 66.7, 79.7, 125.8, 126.0, 126.7, 127.0, 127.7, 128.2, 128.3,
128.4, 129.0, 134.0, 134.8, 136.5, 158.6 ppm. MS (EI): m/z (%) =
356 (2) [M + H], 240 (79), 220 (24), 180 (100), 117 (90), 91 (68),
77 (52). HMRS: [M + H], found 356.16306. C24H22NO2 calcd.
356.16505. C24H21NO2 (355.44): calcd. C 81.10, H 5.96, N 3.94;
found C 80.91, H 5.92, N 3.95.
1
814 (m, Si–C) cm–1. H NMR (500 MHz, CDCl3): δ = –0.46 (s, 3
H, CH3), –0.37 (s, 3 H, CH3), –0.11 (ddd, J = 11.4, 8.3, 5.0 Hz, 1
H, CHCHN), 0.83 (ddd, J = 8.3, 6.3, 5.0 Hz, 1 H, CHHCHN),
1.23 (ddd, J = 11.4, 5.0, 3.4 Hz, 1 H, CHHCHN), 1.81 (d, J =
13.6 Hz, 1 H, CHHPh), 1.85 (d, J = 13.6 Hz, 1 H, CHHPh), 2.37
(ddd, J = 6.3, 5.0, 3.4 Hz, 1 H, CHN), 4.76 (d, J = 8.0 Hz, 1 H,
CHNCO), 5.72 (d, J = 8.0 Hz, 1 H, CHOCO), 6.82–7.18 (m, 15
H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3): δ = –5.3, –4.8, 4.1,
11.6, 24.8, 29.0, 66.9, 79.6, 124.0, 125.9, 127.6, 127.8, 128.0, 128.1,
128.2, 128.3, 134.3, 134.4, 139.4, 158.4 ppm. MS (CI): m/z (%) =
426 (29) [M – H], 382 (100), 308 (26), 238 (16), 195 (57). HMRS:
M – H, found 426.18798. C27H28NO2Si calcd. 426.18892.
C27H29NO2Si: calcd. C 75.84, H 6.84, N 3.38; found C 76.09, H
6.93, N 3.30.
(4R,5S)-3-[(1S,2S)-2-(4-Methoxybenzyl)cyclopropyl]-4,5-diphenyl-
oxazolidin-2-one (41): Mixture of 41, (4S,5R)-3-methyl-4,5-di-
phenyloxazolidin-2-one and (4S,5R)-4,5-diphenyloxazolidin-2-one
(63% yield based on 1H NMR). A pure sample was obtained by
recrystallisation from ethyl acetate/PE; white needles; m.p. 162–
163 °C (EtOAc/PE). [α]1D8 = +57.6 (c = 0.55, CHCl3). IR (film):
ν
= 3267, 3035, 1746, 1512, 1455, 1410, 1351, 1293, 1217 cm–1.
˜
max
cm–1. 1H NMR (500 MHz, CDCl3): δ = 0.92 (ddd, J = 7.2, 6.0,
5.7 Hz, 1 H, CHHCHN), 1.21 (ddddd, J = 9.2, 7.7, 6.0, 5.5, 3.3 Hz,
1 H, CHCH2Ar), 1.29 (ddd, J = 9.2, 5.7, 3.6 Hz, 1 H, CHHCHN),
2.10 (dd, J = 14.5, 7.7 Hz, 1 H, CHHAr), 2.30 (ddd, J = 7.2, 3.6,
3.3 Hz, 1 H, CHNCH2), 2.53 (dd, J = 14.5, 5.5 Hz, 1 H, CHHAr),
3.75 (s, 3 H, OMe), 4.69 (d, J = 7.9 Hz, 1 H, NCHPh), 5.69 (d, J
= 7.9 Hz, 1 H, OCHPh), 6.64 (br. d, J = 8.7 Hz, 2 H, Ar-H), 6.77
(t, J = 6.9 Hz, 2 H, Ph), 6.79 (d, J = 8.7 Hz, 2 H, Ar-H), 6.93–6.96
(m, 2 H, Ph), 7.03–7.12 (m, 6Hϫ, Ph) ppm. 13C NMR (125 MHz,
CDCl3): δ = 14.1, 21.1, 31.0, 36.7, 55.1, 66.7, 79.6, 113.7, 125.9,
127.5, 127.5, 127.7, 128.0, 128.2, 129.1, 132.2, 134.1, 134.2, 157.8,
158.0 ppm. MS (CI): m/z (%) = 400 (22) [M + H], 240 (100), 196
(74), 107 (27). HMRS: [M + H], found 400.19183, C26H26NO3
calcd. 400.19127.
(؎)-(4S,5R)-4,5-Diphenyl-3-[(1S,2S)-2-(trimethylsilyl)cyclopropyl]-
oxazolidin-2-one (38): White solid; m.p. 145–146 °C. IR (film): ν
˜
max
= 3035 (w), 2955 (w), 1734 (s), 1499 (w), 1455 (w), 1409 (m), 1380
(m), 1247 (w), 1200 (m), 1135 (w), 1025 (w) cm–1 1H NMR
.
(300 MHz, CDCl3): δ = –0.30 [s, 9 H, Si(CH3)3], –0.08 (ddd, J =
11.4, 8.2, 5.0 Hz, 1 H, CHCHN), 0.87 (ddd, J = 8.2, 6.2, 4.8 Hz, 1
H, CHHCHN), 1.23 (ddd, J = 11.4, 4.8, 3.2 Hz, 1 H, CHHCHN),
2.39 (ddd, J = 6.2, 5.0, 3.2 Hz, 1 H, CHN), 4.86 (d, J = 8.0 Hz, 1
H, CHNCO), 5.78 (d, J = 8.0 Hz, 1 H, CHNCO), 6.86–7.15 (m,
10 H, Ar-H) ppm. 13C NMR (75 MHz, CDCl3): δ = 5.3, 11.5, 28.9,
66.9, 79.6, 125.9, 127.6, 127.8, 128.2, 128.3, 134.3, 134.4, 158.5
ppm. MS (CI+): m/z (%) = 352 (100) [M + H], 308 (86), 292 (15),
230 (10), 180 (62), 130 (7), 100 (3), 73 (17). HMRS: [M + H], found
352.17348. C21H26NO2Si calcd. 352.17327. C21H25NO2Si (351.52):
calcd. C 71.75, H 7.17, N 3.98; found C 71.92, H 7.18, N 3.98.
(؎)-(4S,5R)-3-[(1S,2S)-2-Benzylcyclopropyl]-4,5-diphenyloxazol-
idin-2-one (42a) and (؎)-(4S,5R)-3-[(1R,2R)-2-Benzylcyclopropyl]-
4,5-diphenyloxazolidin-2-one (42b): Mixture of 42a, 42b and
1
(4S,5R)-3-formyl-4,5-diphenyl-2-oxazolidinone (83% yield by H
NMR). IR (film): ν
= 3064 (w), 3031 (w), 2920 (w), 1756 (s),
˜
max
1606 (w), 1497 (w), 1451 (w), 1405 (m), 1217 (w), 1194 (w), 1137
1
(w), 1079 (w), 1026 (w) cm–1. H NMR (500 MHz, CDCl3): 42a: δ
(؎)-(4S,5R)-4,5-Diphenyl-3-[(1S,2S)-2-(tributylstannyl)cyclopropyl]-
= 0.93 (dt, J = 7.0, 5.9 Hz, 1 H, CHHCHN), 1.24 (m, 1 H,
CHCH2Ph), 1.31 (ddd, J = 9.4, 5.7, 3.7 Hz, 1 H, CHHCHN), 2.18
oxazolidin-2-one (39): White amorphous solid. IR (film): ν
=
˜
max
2959 (s), 2923 (s), 2872 (m), 2849 (m), 1748 (s), 1457 (m), 1374 (m), (dd, J = 14.5, 7.7 Hz, 1 H, CHHPh), 2.31 (dt, J = 7.0, 3.5 Hz, 1
1218 (m), 1025 (w) cm–1. 1H NMR (400 MHz, CDCl3): δ = 0.02
H, CHN), 2.57 (dd, J = 14.5, 5.6 Hz, 1 H, CHHPh), 4.68 (d, J =
(ddd, J = 11.5, 8.3, 5.1 Hz, 1 H, CHCHN), 0.48–0.64 (m, 6 H, 7.9 Hz, 1 H, CHNCO), 5.69 (d, J = 7.9 Hz, 1 H, CHOCO), 6.72–
3ϫCH2), 0.82 (t, J = 7.2 Hz, 9 H, 3ϫCH3), 0.90 (ddd, J = 8.3,
5.9, 5.0 Hz, 1 H, CHHCHN), 1.10–1.33 (m, 13 H, 6ϫCH2 and
CHHCHN), 2.44 (ddd, J = 5.9, 5.1, 3.0 Hz, 1 H, CHN), 4.80 (d,
J = 7.9 Hz, 1 H, CHNCO), 5.73 (d, J = 7.9 Hz, 1 H, CHOCO),
6.86–6.90 (m, 2 H, Ar-H), 6.94–6.99 (m, 2 H, Ar-H), 7.01–7.11 (m,
6.78 (m, 2 H, Ar-H), 6.86–6.97 (m, 4 H, Ar-H), 7.03–7.14 (m, 9 H,
Ar-H); 42b: δ = 0.53 (dt, J = 7.1, 6.2 Hz, 1 H, CHHCHN), 0.85
(ddd, J = 9.4, 5.6, 3.7 Hz, 1 H, CHHCHN), 1.61 (ddddd, J = 9.4,
8.6, 6.2, 5.5, 3.1 Hz, 1 H, CHCH2Ph), 2.29 (dd, J = 14.8, 8.6 Hz,
1 H, CHHPh), 2.35 (dt, J = 7.0, 3.4 Hz, 1 H, CHN), 3.05 (dd, J =
6 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 0.8, 8.3, 11.9, 14.8, 5.5 Hz, 1 H, CHHPh), 4.80 (d, J = 7.9 Hz, 1 H, CHNCO),
13.5, 27.1, 28.7, 29.1, 65.8, 79.7, 125.9, 127.5, 127.7, 127.8, 128.1,
128.2, 134.4, 134.5, 158.4 ppm. MS (EI): m/z (%) = 569 (2) [M+],
512 (64), 398 (3), 332 (6), 288 (9), 234 (32), 180 (100), 143 (6),
5.74 (d, J = 7.9 Hz, 1 H, CHOCO), 6.70–7.15 (m, 15 H, Ar-H)
ppm. 13C NMR (125 MHz, CDCl3): 42a: δ = 14.2, 20.9, 31.2, 37.7,
66.8, 79.7, 126.0, 126.1, 127.6, 127.8, 128.1, 128.2, 128.3, 128.4,
1542
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 1532–1548