PAPER
Intramolecular Aziridination of Allylic Carbamates
2963
Cinnamyl Carbamate (1a)
Yield: 87%; mp 118–120 °C.
IR (KBr): 3422, 1687, 1411, 1344, 1051, 971, 747, 695 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.43–7.28 (m, 5 H), 6.68 (d,
J = 16.2 Hz, 1 H), 6.31 (td, J = 16.2, 6 Hz, 1 H), 4.75 (d, J = 6.6 Hz,
2 H), 4.76–4.68 (m, 2 H).
1H NMR (300 MHz, CDCl3): d = 7.55–7.51 (m, 1 H), 7.37–7.34 (m,
1 H), 7.21–7.19 (m, 2 H), 7.04 (d, J = 15.9 Hz, 1 H), 6.28 (td,
J = 6.0, 15.9 Hz, 1 H), 4.90 (br, 2 H), 4.76 (d, J = 6.0 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 156.59, 134.44, 133.22, 129.71,
129.60, 128.99, 127.00, 126.87, 126.48, 65.44.
MS (EI): m/z (%) = 211 (M+, 12), 168 (28), 151 (15), 133 (69), 115
(100), 103 (19), 91 (19), 44 (16).
HRMS (EI): m/z calcd for C10H10ClNO2 (M+): 211.0400; found:
13C NMR (75 MHz, CDCl3): d = 156.90, 136.18, 133.73, 128.52,
127.94, 126.53, 123.51, 65.56.
211.0398.
MS (EI): m/z (%) = 177 (M+, 25), 134 (43), 115 (100), 105 (17), 92
(63), 78 (18), 63 (7), 44 (17).
HRMS (EI): m/z calcd for C10H11NO2 (M+): 177.0790; found:
177.0792.
(E)-3-(4-Bromophenyl)allyl Carbamate (1f)
Yield: 90%; mp 145–147 °C.
IR (KBr): 3424, 1687, 1487, 1426, 1347, 1066, 970, 847 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.45 (d, J = 8.4 Hz, 2 H), 7.25 (d,
J = 8.4 Hz, 2 H), 6.59 (d, J = 16.2 Hz, 1 H), 6.28 (td, J = 6.6, 16.2
Hz, 1 H), 4.72 (d, J = 6.6 Hz, 2 H), 4.73–4.68 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 156.42, 135.17, 132.55, 131.76,
128.14, 124.40, 121.83, 65.41.
MS (EI): m/z (%) = 255 (M+, 12), 212 (22), 133 (54), 115 (100), 102
(14), 89 (15), 77 (18), 44 (28).
HRMS (EI): m/z calcd for C10H10BrNO2 (M+): 254.9895; found:
254.9897.
Anal. Calcd for C10H11NO2: C, 67.78; H, 6.26; N, 7.90. Found: C,
67.70; H, 6.27; N, 7.80.
(E)-3-p-Tolylallyl Carbamate (1b)
Yield: 91%; mp 151–153 °C.
IR (KBr): 3423, 1685, 1614, 1421, 1346, 1058, 973, 792 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.29 (d, J = 8.1 Hz, 2 H), 7.13 (d,
J = 8.1 Hz, 2 H), 6.62 (d, J = 16.2 Hz, 1 H), 6.24 (td, J = 6.6, 16.2
Hz, 1 H), 4.72 (d, J = 6.6 Hz, 2 H), 4.73–4.68 (m, 2 H), 2.34 (s, 3
H).
13C NMR (75 MHz, CDCl3): d = 156.84, 138.18, 134.19, 133.69,
129.53, 126.76, 122.65, 66.10, 21.45.
Anal. Calcd for C10H10BrNO2: C, 46.90; H, 3.94; N, 5.47. Found: C,
46.83; H, 4.33; N, 5.44.
MS (EI): m/z (%) = 191 (M+, 38), 148 (45), 129 (59), 115 (100), 106
(43), 91 (58), 77 (21), 44 (86).
HRMS (EI): m/z calcd for C11H13NO2 (M+): 191.0946; found:
191.0944.
(E)-3-(4-Fluorophenyl)allyl Carbamate (1g)
Yield: 84%; mp 111–112 °C.
IR (KBr): 3419, 1656, 1509, 1420, 1348, 1230, 1063, 971 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.38–7.33 (m, 2 H), 7.04–6.98 (m,
2 H), 6.62 (d, J = 16.2 Hz, 1 H), 6.21 (td, J = 6.3, 16.2 Hz, 1 H),
4.77–4.71 (m, 2 H), 4.71 (d, J = 6.3 Hz, 2 H).
Anal. Calcd for C11H13NO2: C, 69.09; H, 6.85; N, 7.32. Found: C,
68.80; H, 6.82; N, 7.21.
(E)-3-(4-Chlorophenyl)allyl Carbamate (1c)
Yield: 89%; mp 144–145 °C.
IR (KBr): 3431, 1685, 1606, 1410, 1341, 1079, 751, 702 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.34–7.30 (m, 4 H), 6.60 (d,
J = 15.6 Hz, 1 H), 6.27 (td, J = 6.3, 15.6 Hz, 1 H), 4.73–4.71 (m, 4
13C NMR (75 MHz, CDCl3): d = 162.54 (JC,F = 185 Hz), 156.62,
132.69, 132.38, 128.15 (JC,F = 6 Hz), 123.29, 115.52 (JC,F = 16 Hz),
65.55.
19F NMR (282 MHz, CDCl3): d = –114.21.
MS (EI): m/z (%) = 195 (M+, 20), 152 (43), 133 (100), 115 (20), 109
H).
(42), 96 (21), 75 (13), 44 (26).
13C NMR (75 MHz, CDCl3): d = 156.51, 134.72, 133.66, 132.45,
128.76, 127.77, 124.25, 65.43.
HRMS (EI): m/z calcd for C10H10FNO2 (M+): 195.0696; found:
195.0697.
MS (EI): m/z (%) = 211 (M+, 10), 191 (6), 168 (21), 148 (18), 130
(49), 115 (100), 91 (38), 44 (17).
HRMS (EI): m/z calcd for C10H10ClNO2 (M+): 211.0400; found:
211.0401.
(E)-3-(4-Nitrophenyl)allyl Carbamate (1h)
Yield: 80%; mp 160–161 °C.
1H NMR (300 MHz, CDCl3): d = 8.20 (d, J = 9.0 Hz, 2 H), 7.53 (d,
J = 9.0 Hz, 2 H), 7.72 (d, J = 16.2 Hz, 1 H), 6.47 (dt, J = 5.4, 16.2
Hz, 1 H), 4.78 (d, J = 5.4 Hz, 2 H), 4.73 (br s, 2 H).
13C NMR (75 MHz, CDCl3): d = 156.24, 147.22, 142.70, 130.85,
128.70, 127.12, 124.03, 64.89.
MS (EI): m/z (%) = 222 (M+, 3), 179 (95), 162 (78), 132 (25), 116
(38), 115 (100), 103 (26), 91 (24), 77 (37).
(E)-3-(3-Chlorophenyl)allyl Carbamate (1d)
Yield: 90%; mp 70–72 °C.
1H NMR (300 MHz, CDCl3): d = 7.37 (s, 1 H), 7.23–7.20 (m, 3 H),
6.58 (d, J = 15.6 Hz, 1 H), 6.30 (td, J = 6.3, 15.6 Hz, 1 H), 4.95 (br
s, 2 H), 4.72 (d, J = 6.3 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 156.68, 138.12, 134.55, 132.12,
129.81, 127.93, 126.51, 125.22, 124.79, 65.26.
HRMS (EI): m/z calcd for C10H10N2O4 (M+): 222.0641; found:
222.0642.
MS (EI): m/z (%) = 211 (M+, 15), 168 (31), 133 (22), 126 (50), 116
(30), 115 (100), 103 (22), 77 (28), 44 (57).
HRMS (EI): m/z calcd for C10H10ClNO2 (M+): 211.0400; found:
211.0402.
(E)-3-Phenylbut-2-enyl Carbamate (1i)
Yield: 85%; mp 87–88 °C.
IR (KBr): 3430, 1693, 1616, 1446, 1417, 1351, 1091, 745 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.41 (d, J = 6.9 Hz, 2 H), 7.35–
7.26 (m, 3 H), 5.91 (t, J = 7.2 Hz, 1 H), 4.79 (d, J = 7.2 Hz, 2 H),
4.80–4.74 (m, 2 H), 2.12 (s, 3 H).
(E)-3-(2-Chlorophenyl)allyl Carbamate (1e)
Yield: 91%; mp 120–122 °C.
IR (KBr): 3423, 1687, 1603, 1471, 1341, 1054, 969, 753 cm–1.
Synthesis 2011, No. 18, 2959–2967 © Thieme Stuttgart · New York