5096
References and Notes
1) E. Vedejes and G. R. Martinez, J. Am. Chem. Soc., 102, 7993 (1980); K. Achiwa, T. Motoyama,
and M. Sekiya, Chem. Pharm. Bull., 31, 3939 (1983); T. Livinghouse and R. Smith, J. Org.
Chem., 48, 1554 (1983); A. Padwa, G. Hoffmanns, and M. Tomas, Tetrahedron Lett., 24, 4303
(1983); O. Tsuge, S. Kanemasa, S. Kuraoka, and S. Takenaka, Chem. Len., 1984, 279, 281; A.
Hosomi, Y. Sakata, and H. Sakurai, Chem. Lett., 1984, 1117.
2) A. Padwa, G. E. Fryxell, J. R: Gasdaska, M. K. Venkatramanan, and G. S. K. Wong, J. Org. Chem.,
54, 644 (1989).
3) O. Tsuge, S. Kanemasa, A. Hatada, and K. Matsuda, Bull. Chem. Soc. Jpn., 59, 2537 (1986), and
references cited therein.
4) M. Komatsu, M. Ohno, S. Tsuno, and Y. Ohshiro, Chem. Left., 1990, 575.
5) Spectral data for 2a-¢ are as follows; 2a (trans:cis = 84:16); trans-2a: 1H-NMR (C6D6)~i-0.12
(s, 9H, SiMe3), 3.89 (ddd, J = 1.7, 2.7, 4.6 Hz, 1H, H-4), 4.50 (d, J = 4.6 Hz, 1H, H-5), 4.69 (dd, J =
3.9, 2.7 Hz, 1H, H-3), 6.31 (dd, J = 3.9, 1.7 Hz, 1H, H-2), 6.8-7.3 (m, 10H, Ph); 13C-NMR (C6D6)
ppm -0.4 (SiMe3), 61.1 (d, C-4), 73.0 (d, C-5), 101.7 (d, C-3), 137.4 (d, C-2); cis-2a: 1 H - N M R
(C6D6) 8 0.07 (s, 9H, SiMe3), 4.5 (m, J is not certain, 1H, H-4), 4,7 (m, J is not certain, 1H, H-3),
4.92 (d, J = 11.2 Hz, 1H, H-5), 6.37 (dd, J = 3.9, 2.0 Hz, 1H, H-2); 2b: 1H-NMR (C6D6)8-0.06 (s, 9H,
SiMe3), 3.15 (dd, J = 6.8, 10.5 Hz, 1H, H-5), 3.60 (dd, J = 11.2, 10.5 Hz, 1H, H-5'), 3.94 (dddd, J = 1.9,
2.2, 11.2, 6.8 Hz, 1H, H-4), 4.23 (dd, J=3.7, 2.2 Hz, 1H, H-3), 6.08 (dd, J =3.7, 1.9 Hz, 1H, H-2); 13C-
NMR ( C 6 D 6 ) ppm -0.4 (SiMe3), 49.9 (t, C-5), 56.2 (d, C-4), 103.6 (d, C-3), 137.2 (d, C-2); 2c
(trans:cis = 38:62); trans-2c: 1H-NMR (C6D6) 8 0.07 (s, 9H, SiMe3), 1.67 (dd, J = 1.3, 1.4 Hz, 3H,
Me), 3.74 (ddq, J = 1.6, 4.7, 1.4 Hz, 1H, H-4), 4.68 (d, J = 4.7 Hz, 1H, H-5), 6.21 (dq, J = 1.6, 1.3 Hz,
1H, H-2); cis-2c: 1H-NMR ( C 6 D 6 ) 8 0.11 (s, 9H, SiMe3), 1.76 (dd, J=l.3, 1.4 Hz0 3H, Me), 4.36 (ddq,
J = 1.6, 11.5, 1.4 Hz, 1H, H-4), 5.15 (d, J = 11.5 Hz, 1H, H-5), 6.29 (dq, J = 1.6, 1.3 Hz, 1H, H-2).
6) Spectral data for 3a-c are as follows; 3a: 1H-NMR (CDCI3) 8 2.5-3.4 (m, 3H, H-3, -4), 5.0-5.2
(m, 1H, H-5), 6.1-7.6 (m, 10H, Ph), 7.8-7.9 (m, IH, H-2); 13C-NMR (C6D6) ppm 46.8 (t, C-3), 51.3
(d, C-4), 84.3 (d, C-5), 166.2 (d, C-2); MS (m/z) 221 (M+), 194 (M+-N=CH), 178 (PhC=C-Ph), 144
(M+-Ph), 117 (M+-PhCH=CH2); IR (Nujol) 1604 cm-1; 3b: 1H-NMR (C6D6) 8 2.31-4.45 (m, 5H, H-
3, -4, -5), 6.9-7.5 (m, 5H, Ph), 7.61 (br s, IH, H-2); MS (m/z), 145 (M+); IR (Nujol) 1662 cm-1;
3c (mixture of stereoisomers, 3c1:3e2 = 54:46); 3¢1: 1H-NMR (CDC13) 8 1.22 (d, J = 6.7 Hz, 3H,
Me), 2.9-3.6 (m, 1H, H-3), 3.37 (dd, J = 8.3, 8.3 Hz, 1H, H-4), 5.53 (ddd, J = 8.3, 2.2, 1.9 Hz, 1H, H-5),
6.6-7.5 (m, 10H, Ph), 7.93 (ddd,
J = 1.9, 1.6 Hz,IH, H-2); MS (m/z) 235 (M+); 3e2: 1 H - N M R
(CDCI3) 8 1.22 (d, J = 6.7 Hz, 3H, Me), 2.67 (dd, J = 8.7, 8.7 Hz, 1H, H-4), 2.9-3.6 (m, 1H, H-3), 5.09
(ddd, J = 8.7, 2.6, 2.6 Hz, IH, H-5), 6.6-7.5 (m, 10H, Ph), 7.68 (ddd, J = 2.6, 2.6 Hz, 1H, H-2); MS
(m/z) 235 (M+).
7) O. Tsuge, K. Ueno, and K. Oe, Bull. Chem. Soc. Jpn., 59, 1809 (1986); Heterocycles, 19, 1411
(1982).
8) Spectral data for 6a are as follows; 1H-NMR (CDC13) ~ 3.68 (d, J = 6.5 Hz, 1H, -PhCHCH(CO)-),
3.72 (dd, J = 7.1, 7.8 Hz, 1H, -HNCH(CH=)-), 4.44 (dd, J = 7.8, 6.5 Hz, 1H, -HNCH(CH=)CH-), 5.07
(broad s, 1H, -HNCHPh-), 6.35 (dd, J = 7.1 Hz, 16.3 Hz, 1H, ---CH-), 6.80 (d, J = 16.3 Hz, 1H, PhCH=);
MS (m/z), 394 (M+); IR (KBr), 1714, 1780 cm"1.
(Received in Japan 13 June 1991)