(MHϩ), 265 (Mϩ), 85, 75 (Found: Mϩ, 265.1073. C11H20ClNO4
requires 265.1080).
(S)-N-(3-Chloroprop-1-en-2-yl)-N-(1-phenylethyl)acetamide 22
To a solution of (S)-2 (0.50 g, 3.14 mmol) in DCM (5 ml) was
added acetyl chloride (0.25 ml, 3.52 mmol) and the reaction
mixture stirred at room temperature for 3 hours. Water (10 ml)
was added and the mixture extracted with DCM (3 × 10 ml).
The combined organic extracts were washed with water (2 × 5
ml), dried over MgSO4 and the solvent removed under reduced
pressure. Column chromatography (10% ethyl acetate–light
petroleum) gave (S)-22 (0.50 g, 67%) as a pale yellow oil which
slowly decomposes at room temperature. [α]D Ϫ29.6 (c 1.0,
CHCl3); νmax (film)/cmϪ1 2979, 1670, 1380, 1308, 1110; δH (400
MHz, CDCl3) 7.34–7.25 (5H, m, ArH), 5.99 (1H, br s,
(S)-Methyl N-(3-chloroprop-1-en-2-yl)-N-(1-phenyl-2-phenyl-
methoxy)ethylcarbamate 19
To a solution of (S)-12 (0.20 g, 0.75 mmol) in toluene (5 ml)
was added methyl chloroformate (81 mg, 0.86 mmol) and the
reaction mixture stirred at room temperature for 24 hours.
Water (5 ml) was added and the mixture extracted with diethyl
ether (3 × 10 ml). The combined organic extracts were washed
with water (2 × 5 ml), dried over MgSO4 and the solvent
removed under reduced pressure. Column chromatography
(10% ethyl acetate–light petroleum) gave (S)-19 (0.14 g, 52%) as
a pale yellow oil. [α]D ϩ25.6 (c 1.0, CHCl3); νmax (film)/cmϪ1
3055, 1711, 1654, 1458, 1271; δH (300 MHz, CDCl3) 7.50–7.25
CHCH ), 5.57 (1H, s, ᎐CH), 5.06 (1H, s, ᎐CH), 3.43–3.39 (2H,
᎐
᎐
3
br m, CH2Cl), 2.12 (3H, s, CH3), 1.52 (3H, d, J 7.0, CH3CH),
peak broadening due to amide rotamers; δC (100.6 MHz,
CDCl3) 169.9 (s), 142.2 (s), 140.8 (s), 128.4 (d), 128.1 (d), 127.8
(d), 120.8 (t), 51.5 (d), 45.2 (t), 22.5 (q), 16.8 (q); m/z 239/237
(Mϩ), 202, 105, 77 (Found: Mϩ, 237.0914. C13H16ClNO requires
237.0920).
(10H, m, ArH), 5.47 (1H, s, ᎐CH), 5.42 (1H, dd, J 8.9, 5.5,
᎐
NCHPh), 5.03 (1H, s, ᎐CH), 4.59 (2H, br s, CH Ph), 4.07 (1H,
᎐
2
dd, J 10.1, 8.9, CHOBn), 3.92 (1H, d, J 13.9, CHCl), 3.88 (1H,
dd, J 10.1, 5.5, CHOBn), 3.75 (1H, d, J 13.9, CHCl), 3.71 (3H,
s, OCH3); δC (100.6 MHz, CDCl3) 155.5 (s), 142.3 (s), 138.0 (s),
137.8 (s), 128.5 (d), 128.4 (d), 128.0 (d), 127.8 (d), 127.7 (d),
127.5 (d), 116.3 (t), 73.0 (t), 69.2 (t), 60.8 (d), 52.9 (q), 44.4 (t);
m/z 361/359 (Mϩ), 324 (Mϩ Ϫ Cl), 238, 104, 91, 51 (Found: Mϩ,
359.1297. C20H22ClNO3 requires 359.1288).
(S)-N-(3-Chloroprop-1-en-2-yl)-N-(1-phenylethyl)-4-nitrobenz-
amide 23
To a solution of (S)-2 (0.20 g, 1.26 mmol) in DCM (3.0 ml) was
added p-nitrobenzoyl chloride (0.25 g, 1.35 mmol) dissolved in
DCM (1 ml) and the reaction stirred for 3.5 hours at room
temperature. Water (5 ml) was added and the mixture extracted
with DCM (3 × 10 ml). The combined organic extracts were
washed with water (2 × 5 ml), dried over MgSO4, and the
solvent removed under reduced pressure. Column chromato-
graphy (15% ethyl acetate–light petroleum) gave (S)-23 (0.33 g,
76%) as a yellow oil. [α]D ϩ2.46 (c 1.0, CHCl3); νmax (film)/cmϪ1
1640, 1510, 1350; δH (300 MHz, CDCl3) 8.24 (2H, d, J 7.0,
ArH), 7.67 (2H, d, J 7.0, ArH), 7.41–7.26 (5H, m, ArH), 5.59
(1H, br s, CHCH ), 5.40 (1H, s, ᎐CH), 4.91 (1H, s, ᎐CH), 3.60
(S)-Methyl N-(3-chloroprop-1-en-2-yl)-N-(3-methyl-1-phenyl-
methoxy)butan-2-ylcarbamate 20
To a solution of (S)-13 (0.20 g, 0.86 mmol) in DCM (5 ml) was
added methyl chloroformate (90 mg, 0.95 mmol) and the reac-
tion mixture stirred at room temperature for 24 hours. Water (5
ml) was added and the mixture extracted with diethyl ether
(3 × 10 ml). The combined organic extracts were washed with
water (2 × 5 ml), dried over MgSO4 and the solvent removed
under reduced pressure. Column chromatography (10% ethyl
acetate–light petroleum) gave (S)-20 (0.21 g, 74%) as a colour-
less oil. [α]D Ϫ22.8 (c 1.0, CHCl3); νmax (film)/cmϪ1 2967, 1720,
1654, 1447; δH (300 MHz, CDCl3) 7.36–7.25 (5H, m, ArH), 5.52
᎐
᎐
3
(1H, br d, J 14, CHCl), 3.45 (1H, br d, J 14, CHCl), 1.70 (3H, d,
J 7.0, CH3); δC (100.6 MHz, CDCl3) 168.6 (s), 148.3 (s), 142.5
(s), 141.2 (s), 140.0 (s), 128.6 (d), 128.0 (d), 127.7 (d), 127.5 (d),
126.3 (d), 120.3 (t), 53.8 (d), 44.8 (t), 16.9 (q); m/z 346/344 (Mϩ),
309 (Mϩ Ϫ Cl), 150, 105, 77 (Found: Mϩ, 344.0936. C18H17-
ClN2O3 requires 344.0927).
(1H, s, ᎐CH), 5.29 (1H, s, ᎐CH), 4.51 (1H, d, J 12, A of AB,
᎐
᎐
CHPh), 4.46 (1H, d, J 12, B of AB, CHPh), 4.19 (1H, d, J 13, A
of AB, CHCl), 4.12 (1H, d, J 13, B of AB, CHCl), 3.71–3.57
(3H, m, CH2OBn, NCH), 3.68 (3H, s, OCH3), 2.00–1.98 (1H,
m, CH(CH3)2), 1.00 (3H, d, J 6.7, CH3), 0.94 (3H, d, J 6.7,
CH3); δC (100.6 MHz, CDCl3) 155.5 (s), 143.9 (s), 138.0 (s),
128.3 (d), 127.61 (d), 127.60 (d), 115.1 (t), 72.9 (t), 69.2 (t), 66.4
(d), 52.7 (q), 44.6 (t), 29.0 (d), 20.6 (q), 20.3 (q); m/z 327/325
(Mϩ), 290 (Mϩ Ϫ Cl), 204, 91, 55 (Found: Mϩ, 325.1446.
C17H24ClNO3 requires 325.1444).
Nucleophilic ring opening of (S)-N-(1-phenylethyl)-2-methylene-
aziridine 2 with p-anisoyl chloride
To a stirred solution of (S)-2 (0.31 g, 1.95 mmol) in DCM (4
ml) was added p-anisoyl chloride (0.37 g, 2.17 mmol) dissolved
in DCM (1 ml) and the resulting mixture stirred overnight at
room temperature. The solvent was removed under reduced
pressure to give a crude, cherry coloured oil. Column chroma-
tography (10% ethyl acetate–light petroleum) gave (S)-24 (0.33
g, 51%) as a pale yellow oil. νmax (film)/cmϪ1 3015, 1652, 1607,
1508, 1330, 1253 cmϪ1; δH (400 MHz, CDCl3) 7.45–7.27 (7H, m,
Ar), 6.83 (2H, d, J 8.9, Ar), 6.13 (1H, q, J 7.0, CHCH3), 5.65
(S)-Benzyl N-(3-chloroprop-1-en-2-yl)-N-(1-phenylethyl)-
carbamate 21
To a solution of (S)-2 (0.30 g, 1.88 mmol) in toluene (5 ml) was
added benzyl chloroformate (0.30 ml, 2.10 mmol) and the reac-
tion mixture stirred at room temperature for 24 hours. Water
(10 ml) was added and the mixture extracted with diethyl ether
(3 × 10 ml). The organic layers were collected, washed with
water (2 × 5 ml), dried over MgSO4 and the solvent removed
under reduced pressure. Column chromatography (10% ethyl
acetate–light petroleum) gave (S)-21 (0.39 g, 63%) as a colour-
less oil. [α]D Ϫ3.7 (c 1.0, CHCl3); νmax (film)/cmϪ1 3028, 1710,
1643, 1405, 1317; δH (300 MHz, CDCl3) 7.34–7.25 (10H, m,
(1H, s, ᎐CH), 3.80 (3H, s, OMe), 1.61 (3H, d, J 7.0, CHCH ),
᎐
3
1.49 (3H, s, ᎐CCH ); δ (100.6 MHz, CDCl3) 169.8 (s), 160.9
᎐
3
C
(s), 141.1 (s), 137.9 (s), 129.5 (d), 129.1 (s), 128.5 (d), 127.7 (d),
127.6 (d), 126.6 (d), 113.4 (d), 55.2 (q), 53.3 (d), 19.6 (q), 16.8
(q); m/z 332 (MHϩ 37Cl), 331 (Mϩ 37Cl), 330 (MHϩ 35Cl), 329
(Mϩ 35Cl), 294, 225, 135, 105, 77 (Found: Mϩ, 329.1183. C19H20-
ClNO2 requires 329.1183). Further elution gave (S)-25 (0.21 g,
42%) as a white flaky powder. νmax (DCM)/cmϪ1 3339, 2924,
2853, 1623, 1456, 1377, 1256; δH (300 MHz, CDCl3) 7.75 (2H,
d, J 9.0, Ar), 7.41–7.27 (5H, m, Ar), 6.93 (2H, d, J 9.0, Ar), 6.24
(1H, br s, NH), 5.37 (1H, q, J 7.0, CHCH3), 3.84 (3H, s, OCH3),
1.62 (3H, d, J 7.0, CH3); δC (100.6 MHz, CDCl3) 166.2 (s), 162.1
(s), 143.4 (s), 128.8 (d), 128.7 (d), 127.4 (d), 126.8 (s), 126.3 (d),
113.7 (d), 55.4 (q), 49.1 (d), 21.8 (q); m/z 256 (MHϩ), 255 (Mϩ),
151, 135, 120, 77 (Found: Mϩ, 255.1268. C16H17NO2 requires
255.1260).
ArH), 5.47 (1H, q, J 5.2, CHCH ), 5.39 (1H, s, ᎐CH), 5.18 (1H,
᎐
3
d, J 12.5, CO2CHHPh), 5.12 (1H, d, J 12.5, CO2CHHPh), 4.93
(1H, s, ᎐CH), 3.95 (1H, d, J 14, CHCl), 3.70 (1H, d, J 14,
᎐
CHCl), 1.63 (3H, d, J 5.2, CH3); δC (100.6 MHz, CDCl3) 154.1
(s), 141.7 (s), 141.4 (s), 136.2 (s), 128.5 (d), 128.4 (d), 128.0 (d),
127.7 (d), 127.5 (d), 127.2 (d), 116.0 (t), 67.5 (t), 56.2 (d), 45.0
(t), 17.9 (q); m/z 331/329 (Mϩ), 294, 238, 194, 91, 77, 51 (Found:
Mϩ, 329.1196. C19H20ClNO2 requires 329.1182).
2052
J. Chem. Soc., Perkin Trans. 1, 2000, 2047–2053