PAPER
Regioselective Ring Opening of Aziridines by Amines
2213
EIMS (70 eV): Compound 5a: m/z (%) = 395 (1), 303 (M – Bn, 5),
274 (7), 211 (18), 210 (100), 118 (10), 105 (25), 91 (19).
tert-Butyl trans-2-[(2-Phenylethyl)amino]cyclohexyl}carbam-
ate (12)
Solid; yield: 73%; mp 88 °C; Rf 0.36 (CH2Cl2–MeOH, 95:5).
IR (KBr): 3450, 1700, 1525, 1450, 1370, 1270, 1180 cm–1.
EIMS (70 eV): Compound 6a: m/z (%) = 303 (M – Bn, 2), 135 (10),
134 (100), 132 (12), 106 (42), 105 (41), 91 (21).
N-[2-(Diallylamino)-2-phenylethyl]-4-methylbenzenesulfona-
mide (5b; R1 = R2 = allyl) and N-[2-(Diallylamino)-1-phenyl-
ethyl]-4-methylbenzenesulfonamide (6b; R1 = R2 = allyl)
1H NMR (300 MHz, CDCl3): = 7.35–7.18 (m, 5 H), 4.92–4.70 (m,
2 H), 3.38–3.22 (m, 1 H), 3.15–3.00 (m, 1 H), 2.90–2.72 (m, 4 H),
2.14–1.99 (m, 2 H), 1.78–1.65 (m, 2 H), 1.45 (s, 9 H), 1.40–1.08 (m,
4 H).
13C NMR (75.5 MHz, CDCl3): = 156.1 (s), 139.3 (s), 128.5 (2 d),
128.4 (2 d), 126.2 (d), 79.4 (s), 61.2 (d), 53.8 (d), 47.6 (t), 36.1 (t),
32.6 (t), 30.8 (t), 28.2 (3 q), 24.6 (t), 24.3 (t).
Colorless oil; yield: 80%; 5b/6b = 80:20; Rf 0.83 (hexane–EtOAc,
4:1).
IR (neat): 3290, 1645, 1600, 1455, 1330, 1170, 1095, 910 cm–1.
1H NMR (300 MHz, CDCl3): (5b) = 7.77 (d, J = 8.5 Hz, 2 H),
7.37–7.03 (m, 7 H), 5.79–5.61 (m, 2 H), 5.23 (br s, 1 H), 5.18–5.05
(m, 4 H), 3.88 (dd, J = 10.5, 5.3 Hz, 1 H), 3.36 (dd, J = 12.0, 10.5
Hz, 1 H), 3.22–3.06 (m, 3 H), 2.64–2.40 (m, 2 H), 2.45 (s, 3 H).
EIMS (70 eV): m/z (%) = 261 (M – t-Bu, 1), 245 (M – t-BuO, 8),
227 (23), 171 (57), 154 (10), 153 (100), 127 (22), 110 (15), 105
(16), 98 (14), 81 (20), 59 (22), 57 (13).
1H NMR (300 MHz, CDCl3): (6b) = 7.57 (d, J = 8.1 Hz, 2 H),
7.37–7.03 (m, 7 H), 5.90 (br s, 1 H, 5.79–5.61 (m, 2 H), 5.18–5.05
(m, 4 H), 4.16 (dd, J = 10.7, 4.8 Hz, 1 H), 3.22–3.06 (m, 2 H), 2.83
(dd, J = 14.0, 7.7 Hz, 2 H), 2.64–2.40 (m, 2 H), 2.37 (s, 3 H).
Acknowledgement
Rhodia is gratefully acknowledged for a gift of LiNTf2.
13C NMR (75.5 MHz, CDCl3): (5b + 6b) = 143.3, 143.0, 139.4,
136.6, 136.5, 135.2 (s, CAr), 136.5 (2d, 5b or 6b), 134.2 (2d, 5b or
6b), 129.6, 129.1, 128.4, 128.2, 128.1, 127.9, 127.4, 127.3, 127.0,
126.9 (d, CHAr), 118.3 (2t, 5b or 6b), 117.6 (2t, 5b or 6b), 60.8 (d,
6b), 55.1 (d, 5b), 58.7 (t, 5b), 56.0 (2t, 5b or 6b), 52.2 (2t, 5b or 6b),
43.0 (t, 6b), 21.4, 21.3 (q, 5b, 6b).
References
(1) (a) Padwa, A.; Woolhouse, A. D. In Comprehensive
Heterocyclic Chemistry, Vol. 7; Katritzky, A. R.; Ress, C.
W., Eds.; Pergamon: Oxford, 1984, 47. (b) Kemp, J. E. G.
In Comprehensive Organic Synthesis, Vol. 7; Trost, B. M.;
Fleming, I.; Lwowski, L., Eds.; Pergamon: Oxford, 1991,
469. (c) Mitsunobu, O. In Comprehensive Organic
Synthesis, Vol. 7; Trost, B. M.; Fleming, I.; Ley, S. V., Eds.;
Pergamon: Oxford, 1991, 65.
EIMS (70 eV): Compound 5b: m/z (%) = 369 (M – 1, 1), 187 (16),
186 (100), 144 (3), 117 (2), 104 (6), 91 (17), 65 (3).
EIMS (70 eV): Compound 6b: m/z (%) = 370 (M+, 1), 341, (2), 155
(2), 111 (9), 110 (100), 104 (3), 91 (11), 81 (2), 68 (2).
(2) For reviews, see: (a) Mitsunobu, O. In Comprehensive
Organic Synthesis, Vol. 6; Trost, B. M.; Fleming, I.;
Winterfeldt, E., Eds.; Pergamon: Oxford, 1990, 65.
(b) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599.
(c) Mc Coull, W.; Davis, F. A. Synthesis 2000, 1347.
(3) (a) Duréault, A.; Tranchepain, I.; Depezay, J.-C. J. Org.
Chem. 1989, 54, 5324. (b) Tanner, D.; Birgersson, C.;
Dhaliwal, H. K. Tetrahedron Lett. 1990, 31, 1903.
(c) Bucciarelli, M.; Forni, A.; Moretti, I.; Prati, F.; Torre, G.
Tetrahedron: Asymmetry 1995, 6, 2073. (d) Burgaud, B. G.
M.; Horwell, D. C.; Padova, A.; Pritchard, M. C.
Tetrahedron 1996, 52, 13035. (e) Maligres, P. E.; See, M.
M.; Askin, D.; Reider, P. J. Tetrahedron Lett. 1997, 38,
5253.
4-Methyl-N-{trans-2-[(2-phenylethyl)amino]cyclohexyl}benze-
nesulfonamide (8)
Solid; yield: 87%; mp 128 °C; Rf 0.40 (CH2Cl2–MeOH, 95:5).
IR (KBr): 3445, 1595, 1490, 1455, 1320, 1160, 1085, 810, 750
cm–1.
1H NMR (250 MHz, CDCl3): = 7.71 (d, J = 8.1 Hz, 2 H), 7.35–
7.13 (m, 7 H), 2.93–2.84 (m, 1 H), 2.75–2.49 (m, 4 H), 2.43 (s, 3 H),
2.27–2.18 (m, 1 H), 2.17–1.95 (m, 4 H), 1.78–1.55 (m, 2 H), 1.30–
0.80 (m, 4 H).
13C NMR (60 MHz, CDCl3): = 143.7, 140.1, 137.5 (s), 130.0
(2 d), 129.0 (2 d), 128.9 (2 d), 127.6 (2 d), 126.6 (d), 60.8 (d), 53.9
(d), 47.5 (t), 36.9 (t), 32.9 (t), 31.4 (t), 25.0, (t), 24.8 (t), 21.9 (q).
EIMS (70 eV): m/z (%) = 372 (M+, 1), 282 (18), 281 (100), 218
(11), 217 (67), 200 (37), 155 (13), 105 (32), 98 (10), 96 (35), 91
(36).
(4) (a) Wipf, P.; Uto, Y. Tetrahedron Lett. 1999, 40, 5165.
(b) Prasad, B. A. B.; Sekar, G.; Singh, V. K. Tetrahedron
Lett. 2000, 41, 4677.
(5) (a) Kozikowski, A.; Ishida, H.; Isobe, K. J. Org. Chem.
1979, 44, 2788. (b) Baldwin, J. E.; Adlington, R. M.;
O’Neil, I. A.; Shofield, C.; Spivey, A. C.; Sweeney, J. B. J.
Chem. Soc., Chem. Commun. 1989, 1852. (c)Osborn, H. M.
I.; Sweeney, J. B.; Howson, B. Synlett 1993, 676. (d)Ibuka,
T.; Nakai, K.; Habashita, H.; Fujii, N.; Garrido, F.; Mann,
A.; Chounan, Y.; Yamamoto, Y. Tetrahedron Lett. 1993, 34,
7421. (e) Tanner, D.; Groth, T. Tetrahedron 1997, 53,
16139. (f) Muller, P.; Nury, P. Org. Lett. 1999, 1, 439.
(6) Baldwin, J. E.; Adlington, R. M.; Robinson, N. G. J. Chem.
Soc., Chem. Commun. 1987, 153.
(7) (a) Bonini, C.; Righi, G.; D’Achille, R. Tetrahedron Lett.
1996, 37, 6893. (b) Righi, G.; Franchini, T.; Bonini, C.
Tetrahedron Lett. 1998, 39, 2385. (c) Yadav, J. S.; Subba
Reddy, B. V.; Mahesh Kumar, G. Synlett 2001, 1417.
(d) Sabitha, G.; Satheesh Babu, R.; Rajkumar, M.; Srinivas
Reddy, Ch.; Yadav, J. S. Tetrahedron Lett. 2001, 42, 3955.
(e) Righi, G.; Pietrantonio, S.; Bonini, C. Tetrahedron 2001,
57, 10039.
N-[trans-2-(Diallylamino)cyclohexyl]-4-methylbenzenesulfona-
mide (10)
Colorless oil; yield: 65%; Rf 0.56 (hexane–Et2O, 1:1).
IR (neat): 3220, 1600, 1450, 1320, 1170, 1090, 920 cm–1.
1H NMR (300 MHz, CDCl3): = 7.68 (d, J = 8.1 Hz, 2 H), 7.20 (d,
J = 8.0 Hz, 2 H), 5.87 (br s, 1 H), 5.60–5.42 (m, 2 H), 5.11–4.95 (m,
4 H), 2.88–2.79 (m, 1 H), 2.70–2.52 (m, 3 H), 2.44–2.29 (m, 2 H),
2.35 (s, 3 H), 1.77–1.50 (m, 4 H), 1.22–0.83 (m, 4 H).
13C NMR (75.5 MHz, CDCl3): = 145.0, 137.3 (s, CAr), 130.7
(2 d), 128.6 (2 d, CHAr), 128.4 (2 d, CHAr), 118.5 (2 t), 62.5 (d),
54.9 (d), 53.0 (2 t), 33.6 (t), 26.3 (t), 24.1 (t), 23.9 (t), 21.9 (q).
EIMS (70 eV): m/z (%) = 348 (M+,1), 194 (14), 193 (100), 176 (14),
96 (38), 91 (25).
Synthesis 2002, No. 15, 2211–2214 ISSN 0039-7881 © Thieme Stuttgart · New York