Chatani et al.
1
for major isomer 309 (M+, 0.56), 159 (100), for minor isomer
309 (M+, 0.68), 159 (100); exact mass calcd for C21H27NO
309.2093, found 309.2092 (major isomer), 309.2074 (minor
isomer).
mp 80-82 °C (hexane); Rf 0.24 (hexane/EtOAc 3/1); H NMR
(CDCl3) δ 0.70 (s, 3H), 1.06 (s, 9H), 1.12 (d, J ) 6.2 Hz, 1H),
1.17 (d, J ) 7.6 Hz, 3H), 1.34(s, 3H), 2.15 (dq. J ) 7.6 Hz, J )
1.2 Hz, 1H), 2.20-2.24 (m, 1H), 2.29-2.33 (m, 2H), 2.44-2.48
(m, 1H), 2.50-2.58 (m, 1H), 3.36 (bs, 1H); 13C NMR (CDCl3) δ
15.8, 21.6, 25.4, 26.0, 30.1, 31.6, 39.8, 40.2, 43.3, 50.4, 53.1,
60.7, 133.5, 184.3, 208.9; IR (KBr) 1694 s; MS, m/z (relative
2,3-Dih yd r o-1-(1,1-d im et h ylet h yl)-3-et h yl-3-(4-m et h -
oxyp h en yl)p yr r ol-2-on e (6). Pale yellow solid; mp 72-73 °C
(hexane); Rf 0.50 (hexane/EtOAc 3/1); 1H NMR (CDCl3) δ 0.72
(t, J ) 7.3 Hz, 3H), 1.38 (s, 9H), 1.76-1.98 (m, 2H), 3.68 (s,
3H), 5.42 (d, J ) 5.1 Hz, 1H), 6.65 (d, J ) 5.1 Hz, 1H), 6.76 (d,
J ) 9.2 Hz, 2H), 7.28 (d, J ) 9.2 Hz, 2H); 13C NMR (CDCl3) δ
9.2, 28.3, 31.4, 54.4, 55.1, 58.4, 112.1, 113.6, 127.5, 130.0, 132.5,
158.2, 180.2; IR (KBr) 1682 s; MS, m/z (relative intensity, %)
273 (M+, 18), 188 (100). Anal. Calcd for C17H23NO2: C, 74.69;
H, 8.48; N, 5.12. Found: C, 74.57; H, 8.43; N, 5.09.
2,3-Dih yd r o-1-(1,1-d im eth yleth yl)-3-eth yl-3-(4-tr iflu o-
r om eth ylp h en yl)-p yr r ol-2-on e (8). Clear oil; Rf 0.56 (hex-
intensity, %) 261 (M+, 21), 58 (100); exact mass calcd for C17H27
NO 261.2092, found 261.2087. For another isomer: White
solid; mp 66-68 °C (hexane); Rf 0.07 (hexane/EtOAc 3/1); H
-
1
NMR (CDCl3) δ 0.69 (s, 3H), 1.08 (s, 9H), 1.13 (d, J ) 9.2 Hz,
1H), 1.17 (d, J ) 7.6 Hz, 3H), 1.34(s, 3H), 2.10 (q. J ) 7.6 Hz,
1H), 2.19-2.23 (m, 1H), 2.29-2.34 (m, 2H), 2.47-2.60 (m, 2H),
3.26 (bs, 1H); 13C NMR (CDCl3) δ 16.0, 21.0, 25.4, 26.1, 30.1,
31.6, 40.2, 40.4, 42.8, 50.6, 52.6, 62.1, 133.9, 184.4, 208.5; IR
(KBr) 1694 s; MS, m/z (relative intensity, %) 261 (M+, 19), 58
(100). Anal. Calcd for C17H27NO: C, 78.11; H, 10.41; N, 5.36.
Found: C, 77.82; H, 10.14; N, 5.31.
6,7,8,9-Te t r a h yd r o-5-e t h yl-5H -p yr r olo[2,1-a ]isoin -
d ole (28). Dark brown oil; Rf 0.67 (hexane/EtOAc 3/1); 1H
NMR (CDCl3) δ 0.67 (t, J ) 7.3 Hz, 3H), 1.67-1.80 (m, 5H),
1.82-2.00 (m, 1H), 2.18-2.20 (m, 2H), 2.33-2.39 (m, 2H), 4.33
(bs, 1H), 5.77 (d, J ) 3.2 Hz, 1H), 6.20 (dd, J ) 3.2 Hz, J ) 2.7
Hz, 1H), 6.80 (d, J ) 2.7 Hz, 1H); 13C NMR (CDCl3) δ 7.6, 21.9,
22.4, 22.8, 23.2, 25.6, 64.8, 94.0, 110.4, 115.1, 120.1, 137.4,
142.2; IR (neat) 2928 s, 1470 m; MS, m/z (relative intensity,
%) 187 (M+, 72), 172 (100). Anal. Calcd for C13H17N: C, 83.37;
H, 9.15; N, 7.48. Found: C, 83.17; H, 9.00; N, 7.46.
1
ane/EtOAc 3/1); H NMR (CDCl3) δ 0.71 (t, J ) 7.3 Hz, 3H),
1.37 (s, 9H), 1.84-1.99 (m, 2H), 5.45 (d, J ) 5.4 Hz, 1H), 6.71
(d, J ) 5.4 Hz, 1H), 7.45-7.52 (m, 5H); 13C NMR (CDCl3) δ
9.0, 28.2, 31.5, 54.6, 59.1, 111.3, 124.2 (q, J ) 271.0 Hz, CF3),
125.0-125.6 (complex, Ar), 127.1, 129.0 (q, J ) 32.4 Hz, Ar),
131.0, 144.6, 179.4; IR (neat) 1698 s; MS, m/z (relative
intensity, %) 311 (M+, 4), 57 (100); exact mass calcd for
C
17H20F3NO 311.1497, found 311.1486.
2,3-Dih yd r o-3-bu tyl-1-(1,1-d im eth yleth yl)-3-eth ylp yr -
r ol-2-on e (10). Clear oil; Rf 0.60 (hexane/EtOAc 3/1); 1H NMR
(CDCl3) δ 0.71 (t, J ) 7.3 Hz, 3H), 0.84 (t, J ) 7.0 Hz, 3H),
0.99-1.29 (m, 4H), 1.44 (s, 9H), 1.46-1.68 (m, 4H), 5.08 (d, J
) 2.7 Hz, 1H), 6.61 (d, J ) 2.7 Hz, 1H); 13C NMR (CDCl3) δ
8.7, 14.0, 23.1, 26.5, 28.3, 29.8, 36.5, 54.2, 56.1, 111.8, 129.6,
181.9; IR (neat) 1698 s; MS, m/z (relative intensity, %) 223
(M+, 5), 110 (100). Anal. Calcd for C14H25NO: C, 75.28; H,
11.28; N, 6.27. Found: C, 75.00; H, 11.13; N, 6.14.
Ack n ow led gm en t. This work was supported, in
part, by grants from Monbusho and the Strategic
Research Base “Handai Frontier Research Center”
sponsored by the J apanese Government’s Special Co-
ordination Fund for Promoting Science and Technology.
We also acknowledge the Instrumental Analysis Center,
Faculty of Engineering, Osaka University, for assistance
in obtaining HRMS and elemental analyses.
2,3-Dih yd r o-1-(1,1-d im eth yleth yl)-3-eth yl-4-m eth yl-3-
p h en ylp yr r ol-2-on e (12). Clear oil; Rf 0.49 (hexane/EtOAc
3/1); 1H NMR (CDCl3) δ 0.78 (t, J ) 7.6 Hz, 3H), 1.47 (s, 9H),
1.56 (d, J ) 1.6 Hz, 3H), 1.81-1.94 (m, 1H), 2.21-2.34 (m,
1H), 6.46 (d, J ) 1.6 Hz, 1H), 7.18-7.32 (m, 5H); 13C NMR
(CDCl3) δ 8.3, 10.9, 25.5, 28.3, 54.2, 61.3, 120.6, 125.1, 126.2,
126.6, 128.3, 139.7, 180.4; IR (neat) 1698 s; MS, m/z (relative
Su p p or tin g In for m a tion Ava ila ble: Text listing full
characterization of all of new compounds obtained and figures
showing 1H NMR spectra for aldimine 7, products 4, 8, and
25. This material is available free of charge via the Internet
at http://pubs.acs.org.
intensity, %) 257 (M+, 13), 172 (100). Anal. Calcd for C17H23
-
NO: C, 79.33; H, 9.01; N, 5.44. Found: C, 79.05; H, 8.84; N,
5.30.
2,3,4,5,6,7-Hexah ydr o-3-(1,1-dim eth yleth ylam in o)-2,5,5-
tr im eth yl-1H-4,6- m eth a n oin d e-1-on e (25). The reaction of
imine 24 gives two isomers of 25. For one isomer: White solid;
J O026001M
7018 J . Org. Chem., Vol. 67, No. 20, 2002