4918 J . Org. Chem., Vol. 65, No. 16, 2000
Chatani et al.
(CDCl3) δ 1.20 (t, J ) 7.1 Hz, 6H), 3.16 (s, 2H, 3-H), 3.41 (s,
2H), 4.16 (q, J ) 7.1 Hz, 4H), 5.51 (s, 1H), 5.52 (s, 1H), 7.24
(d, J ) 8.2 Hz, 1H), 7.35-7.45 (m, 2H), 7.65 (d, J ) 8.2 Hz,
1H), 7.76 (d, J ) 7.3 Hz, 1H), 8.43 (d, J ) 8.2 Hz, 1H); 13C
NMR (CDCl3) δ 13.9, 35.7, 39.2, 55.4, 61.5, 117.6, 124.9, 125.1,
126.0, 126.4, 127.6, 128.3, 129.8, 131.8, 132.3, 133.1, 138.2,
170.8; IR (neat) 1740 s, 1636 m, 1600 m; MS, m/z (rel intensity
%) 338 (M+, 10), 191 (100); exact mass calcd for C21H22O4
338.1518, found 338.1525
1,2-Dih yd r o-4-m et h yl-2,2-p h en a n t h r en ed ica r b oxylic
Acid Dieth yl Ester (17): white solid; mp 102-104 °C (hex-
ane/EtOAc ) 4/1); Rf 0.15 (hexane/EtOAc ) 10/1); 1H NMR
(CDCl3) δ 1.17 (t, J ) 7.1 Hz, 6H), 2.51 (d, J ) 1.3 Hz, 3H),
3.45 (s, 2H), 4.09-4.18 (m, 4H), 6.22 (s, 1H), 7.36 (d, J ) 8.3
Hz, 1H), 7.39-7.46 (c, 2H), 7.70 (d, J ) 8.3 Hz, 1H), 7.78-
7.81 (m, 1H), 8.22 (d, J ) 8.2 Hz, 1H); 13C NMR (CDCl3) δ
13.9, 24.2, 36.8, 54.2, 61.6, 124.6, 124.7, 125.4, 125.8, 126.4,
128.4, 128.9, 130.0, 131.4, 132.8, 134.0, 135.8, 170.3; IR (KBr)
1736 s; MS, m/z (rel intensity, %) 338 (M+, 11), 193 (100). Anal.
Calcd for C21H22O4: C, 74.54; H, 6.55. Found: C, 74.33; H,
6.55.
170.4; IR (neat) 1738 s; MS, m/z (rel intensity, %) 360 (M+, 2),
73 (100); exact mass calcd for C20H28O4Si 360.1757, found
360.1758.
2,3-Dih yd r o-1H -8-m et h oxy-5-m et h yl-2,2-b en zocyclo-
h ep ten ed ica r boxylic Acid Dieth yl Ester (24a ): colorless
liquid; bp 100-110 °C/2 mmHg; Rf 0.29 (hexane/EtOAc ) 5/1);
1H NMR (CDCl3) δ 1.26 (t, J ) 7.1 Hz, 6H), 2.06 (s, 3H), 2.30
(d, J ) 6.9 Hz, 2H), 3.07 (s, 2H), 3.81 (s, 3H), 4.19 (q, J ) 7.1
Hz, 4H), 5.90 (t, J ) 6.9 Hz, 1H), 6.82 (dd, J ) 8.6, 2.6 Hz,
1H), 6.89 (d, J ) 2.6 Hz, 1H), 7.18 (d, J ) 8.6 Hz, 1H); 13C
NMR (CDCl3) δ 14.0, 22.2, 31.0, 37.9, 55.1, 61.2, 67.4, 112.1,
115.9, 122.5, 127.0, 133.8, 137.8, 138.4, 158.0, 171.2; IR (neat)
1734 s, 1612 s; MS, m/z (rel intensity %) 332 (M+, 17), 185
(100). Anal. Calcd for C19H24O5: C, 68.66; H, 7.28. Found: C,
68.68; H, 7.19.
2,3-Dih yd r o-1H -6-m et h oxy-5-m et h yl-2,2-b en zocyclo-
h ep ten d ica r boxylic Acid Dieth yl Ester (24b): colorless
liquid; bp 100-110 °C/2 mmHg; Rf 0.29 (hexane/EtOAc ) 5/1);
1H NMR (CDCl3) δ 1.26 (c, 6H), 2.10 (c, 4H), 2.51 (br, 1H),
2.96 (br, 1H), 3.15 (br, 1H), 3.82 (s, 3H), 4.21 (br, 4H), 5.98 (t,
J ) 6.6 Hz, 1H), 6.83 (d, J ) 7.9 Hz, 1H), 6.93 (d, J ) 7.9 Hz,
1H), 7.16 (t, J ) 7.9 Hz, 1H); 13C NMR (CDCl3) δ 14.0, 21.7,
30.7, 37.7, 55.4, 61.3, 66.8, 109.8, 122.9, 124.8, 127.7, 129.3,
137.4, 137.9, 156.7, 171.1; IR (neat) 1733 s, 1600 w; MS, m/z
(rel intensity %) 332 (M+, 10), 185 (100); exact mass calcd for
1,2-Dih yd r o-7-ch lor o-4-m eth yl-2,2-n a p h th a len ed ica r -
boxylic Acid Dieth yl Ester (19): white solid; mp 46-48 °C
(hexane/EtOAc ) 4/1); Rf 0.36 (hexane/EtOAc ) 5/1); 1H NMR
(CDCl3) δ 1.22 (t, J ) 7.1 Hz, 6H), 2.11 (d, J ) 1.3 Hz, 3H),
3.32 (s, 2H), 4.11-4.23 (m, 4H), 5.97 (s, 1H), 7.17 (c, 3H); 13
C
C
19H24O5 332.1614, found 332.1628.
NMR (CDCl3) δ 14.0, 19.3, 34.3, 54.6, 61.8, 121.8, 124.7, 126.9,
127.7, 132.0, 133.3, 134.1, 134.8, 170.1; IR (neat) 1737 s, 1597
m; MS, m/z (rel intensity %) 322 (M+ for 35Cl), 177 (100). Anal.
Calcd for C17H19O4Cl: C, 63.26; H, 5.93; Cl, 10.98. Found: C,
63.21; H, 5.88; Cl, 10.96.
1,2-Dih yd r o-7-m et h oxy-1-m et h yl-1-n a p h t h a len eca r -
boxylic Acid Eth yl Ester (26a ): colorless oil; bp 70-75 °C/2
mmHg; Rf 0.06 (hexane/EtOAc ) 30/1); 1H NMR (CDCl3) δ 1.21
(t, J ) 7.3 Hz, 3H), 1.50 (s, 3H), 2.24 (ddd, J ) 16.8, 4.3, 1.7
Hz, 1H), 2.96 (ddd, J ) 16.8, 4.3, 1.7 Hz, 1H), 3.80 (s, 3H),
4.14 (q, J ) 7.3 Hz, 2H), 5.84 (dt, J ) 9.6, 4.3 Hz, 1H), 6.43 (d,
J ) 9.6 Hz, 1H), 6.72-6.78 (c, 2H), 7.01 (d, J ) 7.9 Hz, 1H);
13C NMR (CDCl3) δ 14.0, 23.9, 34.3, 46.4, 55.0, 60.8, 111.4,
112.3, 123.3, 126.0, 127.4, 139.2, 158.9, 176.1; IR (neat) 1728
s, 1612 s; MS, m/z (rel intensity %) 246 (M+, 7), 173 (100).
Anal. Calcd for C15H18O2: C, 73.15; H 7.37. Found: C, 73.23;
H, 7.17.
1,2-Dih yd r o-5-m et h oxy-1-m et h yl-1-n a p h t h a len eca r -
boxylic Acid Eth yl Ester (26b). The 1H NMR spectrum of
26b was obtained from a 1.2:1 mixture of 26a and 26b: 1H
NMR (CDCl3) δ 3.83 (s, 3H), 5.93-6.00 (dt, J ) 9.9, 4.3 Hz,
1H), 5.96 (dt, J ) 9.9 Hz, 4.3 Hz, 1H), 6.87 (d, J ) 9.9 Hz,
1H), 7.16 (t, J ) 8.1 Hz, 1H).
(Z)-1,2,3,4-Tet r a h yd r o-4-[(t r im et h ylsilyl)m et h ylen e]-
n a p h th a len e-2,2-d ica r boxylic Acid Dieth yl Ester (21Z):
pale yellow oil; bp 110-120 °C/3 mmHg; Rf 0.38 (hexane/EtOAc
1
) 5/1); H NMR (CDCl3) δ 0.07 (s, 9H), 1.22 (t, J ) 7.1 Hz,
6H), 3.06 (d, J ) 1.3 Hz, 2H), 3.29 (s, 2H), 4.15 (q, J ) 7.1 Hz,
4H), 5.58 (t, J ) 1.3 Hz, 1H), 7.13-7.22 (c, 3H), 7.38 (d, J )
7.3 Hz, 1H); 13C NMR (CDCl3) δ 0.6, 14.2, 35.2, 43.0, 55.3, 61.5,
125.3, 127.3, 128.2, 128.3, 129.2, 134.8, 136.0, 149.0, 170.6;
IR (neat) 1738 s, 1608 m; MS m/z (rel intensity, %) 360 (M+,
2), 73 (100); exact mass calcd for C20H28O4Si 360.1757, found
360.1760.
(E)-1,2,3,4-Tet r a h yd r o-4-[(t r im et h ylsilyl)m et h ylen e]-
n a p h th a len e-2,2-d ica r boxylic Acid Dieth yl Ester (21E).
The 1H NMR spectrum of 21E was obtained from a 86:14
mixture of 21Z and 21E: 1H NMR (CDCl3) δ 0.00 (s, 9H), 3.15
(t, J ) 0.7 Hz, 2H), 3.34 (s, 2H), 5.77 (s, 1H); MS m/z (rel
intensity, %) 360 (M+, 5), 75 (100).
1,2-Dih yd r o-4-m et h yl-8-(t r im et h ylsilyl)-2,2-n a p h t h a -
len ed ica r boxylic Acid Dieth yl Ester (22): colorless oil; bp
80-90 °C/2 mmHg; Rf 0.54 (hexane/EtOAc ) 4/1); 1H NMR
(CDCl3) δ 0.39 (s, 9H), 1.23 (t, J ) 7.1 Hz, 6H), 2.15 (d, J )
1.7 Hz, 3H), 3.45 (s, 2H), 4.18 (q, J ) 7.1 Hz, 4H), 5.98 (s,
1H), 7.22 (t, J ) 7.3 Hz, 1H), 7.31 (d, J ) 7.3 Hz, 1H), 7.39 (d,
J ) 7.3 Hz, 1H); 13C NMR (CDCl3) δ -0.1, 14.0, 19.8, 34.8,
54.9, 61.6, 121.0, 124.6, 126.1, 133.8, 133.1, 135.3, 137.6, 138.1,
Ack n ow led gm en t. Support from Monbusho (Grant-
in-Aid for Scientific Research on Priority Areas, No. 706,
Dynamic Control of Stereochemistry) is gratefully ac-
knowledged.
Su p p or tin g In for m a tion Ava ila ble: Full characteriza-
tion data for all new compounds. This material is available
J O000255V