G. Onodera et al. / Tetrahedron 66 (2010) 9021e9031
9027
J¼7.3 Hz, 1H), 7.25 (t, J¼7.3 Hz, 1H), 7.47 (t, J¼7.8 Hz, 2H), 7.56 (t,
J¼7.8 Hz, 1H), 7.60 (d, J¼7.3 Hz, 1H), 7.99 (d, J¼7.8 Hz, 2H). 13C NMR
(s, 9H), 2.95 (s, 6H), 3.03 (dd, J¼15.6 and 4.1 Hz,1H), 3.58 (dd, J¼15.6
and 8.7 Hz, 1H), 5.31 (dd, J¼8.7 and 4.1 Hz, 1H), 6.72 (d, J¼8.7, Hz,
2H), 7.30 (d, J¼8.7 Hz, 2H), 7.45 (t, J¼7.8 Hz, 2H), 7.55 (t, J¼7.8 Hz,
(125 MHz, CDCl3)
d
ꢀ0.2 (3C), 19.0, 48.2, 68.4, 125.9, 126.1, 127.0,
128.39 (2C), 128.43 (2C), 130.2, 132.9, 133.3, 137.6, 142.8, 198.5.
1H), 7.98 (d, J¼7.8 Hz, 2H). 13C NMR (125 MHz, CDCl3)
d 0.0 (3C),
HRMS: calcd for C19H24O2Si ([M]þ), 312.1546. Found: m/z 312.1555.
40.6 (2C), 49.7, 71.5, 112.3 (2C), 126.6 (2C), 128.36 (2C), 128.38 (2C),
132.5, 132.8, 137.7, 149.9, 198.8. HRMS: calcd for C20H28NO2Si
([MþH]þ), 342.1889. Found: m/z 342.1900.
4.3.7. 3-(20,60-Dimethylphenyl)-1-phenyl-3-trimethylsilyloxy-1-
propanone (3fa). 1H NMR (500 MHz, CDCl3, CHCl3)
d
ꢀ0.08 (s, 9H),
2.44 (br s, 3H), 2.62 (br s, 3H), 2.88 (dd, J¼15.4 and 3.2 Hz, 1H), 3.91
(dd, J¼15.4 and 9.6 Hz, 1H), 5.83 (dd, J¼9.6 and 3.2 Hz, 1H), 7.01 (br
s, 2H), 7.07 (t, J¼7.3 Hz, 1H), 7.48 (t, J¼7.3 Hz, 2H), 7.57 (t, J¼7.3 Hz,
4.3.14. 3-(1-Naphthyl)-1-phenyl-3-trimethylsilyloxy-1-propanone
(3ma). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.09 (s, 9H), 3.19 (dd,
J¼16.0 and 2.3 Hz, 1H), 3.76 (dd, J¼16.0 and 9.2 Hz, 1H), 6.29 (dd,
J¼9.2 and 2.3 Hz, 1H), 7.48 (t, J¼7.8 Hz, 2H), 7.53e7.62 (m, 4H), 7.84
(d, J¼7.8 Hz, 1H), 7.88 (d, J¼7.3 Hz, 1H), 7.94 (d, J¼8.2 Hz, 1H), 8.05
(d, J¼7.3 Hz, 2H), 8.28 (d, J¼8.7 Hz, 1H). 13C NMR (125 MHz, CDCl3)
1H), 8.00 (d, J¼7.3 Hz, 2H). 13C NMR (125 MHz, CDCl3)
d
ꢀ0.4 (3C),
20.8 (br, 2C), 45.3, 68.6, 126.9, 128.2 (br), 128.3 (2C), 128.4 (2C),
130.3 (br), 132.8, 134.1 (br), 137.1 (br), 137.7, 139.6, 198.7. HRMS:
calcd for C20H25O2Si ([MꢀH]þ), 325.1624. Found: m/z 325.1617.
d
ꢀ0.1 (3C), 48.7, 68.8, 122.8, 123.3, 125.39, 125.43, 126.1, 127.7, 128.3
(2C), 128.4 (2C), 128.9, 129.6, 132.9, 133.7, 137.5, 140.3, 198.5. HRMS:
4.3.8. 3-(40-Methoxyphenyl)-1-phenyl-3-trimethylsilyloxy-1-prop-
calcd for C22H25O2Si ([MþH]þ), 349.1624. Found: m/z 349.1629.
anone (3ga). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.0 (s, 9H), 3.03
(dd, J¼15.6 and 4.1 Hz, 1H), 3.55 (dd, J¼15.6 and 8.5 Hz, 1H), 3.78 (s,
3H), 5.34 (dd, J¼8.5 and 4.1 Hz, 1H), 6.88 (d, J¼8.7 Hz, 2H), 7.34 (d,
J¼8.7 Hz, 2H), 7.44 (t, J¼7.3 Hz, 2H), 7.54 (t, J¼7.3 Hz, 1H), 7.96 (d,
4.3.15. 3-(2-Naphthyl)-1-phenyl-3-trimethylsilyloxy-1-propanone
(3na). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.02 (s, 9H), 3.13 (dd,
J¼15.6 and 3.7 Hz, 1H), 3.67 (dd, J¼15.6 and 9.0 Hz, 1H), 5.59
J¼7.3 Hz, 2H). 13C NMR (125 MHz, CDCl3)
ꢀ0.1 (3C), 49.6, 55.1, 71.3,
d
(dd, J¼9.0 and 3.7 Hz, 1H), 7.45e7.61 (m, 6H), 7.85e7.89 (m, 4H),
113.6 (2C), 126.9 (2C), 128.3 (2C), 128.4 (2C), 132.9, 136.8, 137.5,
158.8, 198.5. HRMS: calcd for C19H23O3Si ([MꢀH]þ), 327.1416.
Found: m/z 327.1422.
8.01 (d, J¼7.3 Hz, 2H). 13C NMR (125 MHz, CDCl3)
d
ꢀ0.1 (3C), 49.6,
71.8, 124.0, 124.3, 125.7, 126.1, 127.7, 127.9, 128.1, 128.37 (2C), 128.44
(2C), 132.9, 133.0, 133.2, 137.5, 142.1, 198.4. HRMS: calcd for
C22H24O2Si ([M]þ), 348.1546. Found: m/z 348.1539.
4.3.9. 3-(40-Acetylphenyl)-1-phenyl-3-trimethylsilyloxy-1-prop-
anone (3ha). 1H NMR (500 MHz, CDCl3, CHCl3)
d
ꢀ0.03 (s, 9H), 2.57
4.3.16. 3-(2-Furyl)-1-phenyl-3-trimethylsilyloxy-1-propanone
(s, 3H), 3.01 (dd, J¼16.0 and 4.1 Hz, 1H), 3.54 (dd, J¼16.0 and 8.7 Hz,
(3pa). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.03 (s, 9H), 3.29 (dd,
1H), 5.44 (dd, J¼8.7 and 4.1 Hz, 1H), 7.43 (t, J¼7.8 Hz, 2H), 7.50e7.54
J¼16.0 and 4.6 Hz, 1H), 3.64 (dd, J¼16.0 and 8.2 Hz, 1H), 5.41 (dd,
J¼8.2 and 4.6 Hz, 1H), 6.24 (d, J¼3.2 Hz, 1H), 6.31 (dd, J¼3.2 and
1.8 Hz, 1H), 7.36 (d, J¼1.8 Hz, 1H), 7.46 (t, J¼7.3, Hz, 2H), 7.56 (t,
J¼7.3 Hz, 1H), 7.98 (d, J¼7.3 Hz, 2H). 13C NMR (125 MHz, CDCl3)
(m, 3H), 7.93 (d, J¼8.3 Hz, 4H). 13C NMR (125 MHz, CDCl3)
d
ꢀ0.2
(3C), 26.5, 49.2, 71.0, 125.8 (2C), 128.3 (2C), 128.4 (2C), 128.5 (2C),
133.1, 136.2, 137.2, 150.1, 197.6, 197.8. HRMS: calcd for C20H24O3Si
([M]þ), 340.1495. Found: m/z 340.1487.
d
ꢀ0.2 (3C), 45.4, 64.9, 106.1, 110.1, 128.3 (2C), 128.5 (2C), 133.1,
137.3, 141.8, 156.0, 197.8. HRMS: calcd for C16H20O3Si ([M]þ),
4.3.10. 3-(40-Methoxycarbonylphenyl)-1-phenyl-3-trimethylsilyloxy-
288.1182. Found: m/z 288.1178.
1-propanone (3ia). 1H NMR (500 MHz, CDCl3, CHCl3)
d
ꢀ0.04 (s,
9H), 3.00 (dd, J¼15.6 and 4.1 Hz, 1H), 3.55 (dd, J¼15.6 and 8.7 Hz,
1H), 3.88 (s, 3H), 5.44 (dd, J¼8.7 and 4.1 Hz, 1H), 7.43 (t, J¼7.3 Hz,
2H), 7.49 (d, J¼8.2 Hz, 2H), 7.53 (t, J¼7.3 Hz, 1H), 7.94 (d, J¼7.3 Hz,
4.3.17. 1-Phenyl-3-(2-thienyl)-3-trimethylsilyloxy-1-propanone
(3qa). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.05 (s, 9H), 3.20 (dd,
J¼16.0 and 4.1 Hz, 1H), 3.67 (dd, J¼16.0 and 8.2 Hz, 1H), 5.70
(dd, J¼8.2 and 4.1 Hz, 1H), 6.94 (dd, J¼5.0 and 3.7, Hz, 1H), 6.98 (dd,
J¼3.7 and 0.9 Hz, 1H), 7.22 (dd, J¼5.0 and 0.9 Hz, 1H), 7.46 (t,
J¼7.3 Hz, 2H), 7.56 (t, J¼7.3 Hz, 1H), 7.98 (d, J¼7.3 Hz, 2H). 13C NMR
2H), 8.01 (d, J¼8.2 Hz, 2H). 13C NMR (125 MHz, CDCl3)
d
ꢀ0.2 (3C),
49.2, 51.9, 71.1, 125.7 (2C), 128.3 (2C), 128.4 (2C), 129.2, 129.7 (2C),
133.0, 137.3, 149.9, 166.8, 197.8. HRMS: calcd for C20H24O4Si ([M]þ),
356.1444. Found: m/z 356.1452.
(125 MHz, CDCl3)
d
ꢀ0.2 (3C), 49.6, 67.6, 123.0, 124.1, 126.4, 128.3
(2C), 128.4 (2C), 133.0, 137.3, 149.1, 197.7. HRMS: calcd for
4.3.11. 3-(40-Cyanophenyl)-1-phenyl-3-trimethylsilyloxy-1-prop-
C16H19O2SSi ([MꢀH]þ), 303.0875. Found: m/z 303.0877.
anone (3ja). 1H NMR (500 MHz, CDCl3, CHCl3)
d
ꢀ0.01 (s, 9H), 3.02
(dd, J¼16.0 and 4.1 Hz, 1H), 3.53 (dd, J¼16.0 and 8.2 Hz, 1H), 5.44
(dd, J¼8.2 and 4.1 Hz, 1H), 7.45 (t, J¼7.3 Hz, 2H), 7.54 (d, J¼8.5 Hz,
2H), 7.56 (t, J¼7.3 Hz, 1H), 7.63 (d, J¼8.5 Hz, 2H), 7.93 (d, J¼7.3 Hz,
4.3.18. (4E)-1,5-Diphenyl-3-trimethylsilyloxy-4-penten-1-one
(3ra). 1H NMR (500 MHz, CDCl3, TMS)
d
0.17 (s, 9H), 3.13 (dd, J¼15.6
and 4.8 Hz, 1H), 3.51 (dd, J¼15.6 and 7.8 Hz, 1H), 5.07e5.11 (m, 1H),
6.39 (dd, J¼15.6 and 6.0 Hz, 1H), 6.72 (d, J¼15.6 Hz, 1H), 7.32 (t,
J¼7.3 Hz, 1H), 7.41 (t, J¼7.3 Hz, 2H), 7.47 (d, J¼7.3 Hz, 2H), 7.55 (t,
J¼7.3 Hz, 2H), 7.65 (t, J¼7.3 Hz, 1H), 8.07 (d, J¼7.3 Hz, 2H). 13C NMR
2H). 13C NMR (125 MHz, CDCl3)
126.5 (2C), 128.3 (2C), 128.5 (2C), 132.2 (2C), 133.3, 137.1, 150.2,
197.5. HRMS: calcd for C19H21NO2Si ([M]þ), 323.1342. Found: m/z
323.1348.
d
ꢀ0.2 (3C), 49.2, 70.8, 111.2, 118.8,
(125 MHz, CDCl3)
d 0.1 (3C), 47.1, 70.3, 126.5 (2C), 127.5, 128.4 (2C),
128.48 (2C), 128.53 (2C), 129.5, 132.0, 133.0, 136.7, 137.5, 198.4.
HRMS: calcd for C20H23O2Si ([MꢀH]þ), 323.1467. Found: m/z
323.1458.
4.3.12. 3-(40-Nitrophenyl)-1-phenyl-3-trimethylsilyloxy-1-prop-
anone (3ka). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.0 (s, 9H), 3.05
(dd, J¼16.0 and 4.4 Hz, 1H), 3.56 (dd, J¼16.0 and 8.2 Hz, 1H), 5.50
(dd, J¼8.2 and 4.4 Hz, 1H), 7.46 (t, J¼7.3 Hz, 2H), 7.57 (t, J¼Hz, 1H),
7.60 (d, J¼8.7 Hz, 2H), 7.94 (d, J¼7.3 Hz, 2H), 8.20 (d, J¼8.7 Hz, 2H).
4.3.19. (4E,6E)-1-Phenyl-3-trimethylsilyloxy-4,6-octadien-1-one
(3sa). 1H NMR (500 MHz, CDCl3, CHCl3)
d 0.03 (s, 9H), 1.74 (d,
13C NMR (125 MHz, CDCl3)
d
ꢀ0.1 (3C), 49.2, 70.6, 123.7 (2C), 126.6
J¼6.4 Hz, 3H), 2.92 (dd, J¼15.6 and 5.0 Hz, 1H), 3.33 (dd, J¼15.6 and
7.8 Hz, 1H), 4.80e4.84 (m, 1H), 5.62 (dd, J¼15.1 and 6.0 Hz, 1H), 5.70
(dq, J¼15.1 and 6.4 Hz, 1H), 6.02 (dd, J¼15.1 and 10.5 Hz, 1H), 6.20
(dd, J¼15.1 and 10.5 Hz, 1H), 7.44 (t, J¼7.3 Hz, 2H), 7.54 (t, J¼7.3 Hz,
(2C), 128.3 (2C), 128.6 (2C), 133.3, 137.1, 147.2, 152.3, 197.4. HRMS:
calcd for C18H21NO4Si ([M]þ), 343.1240. Found: m/z 343.1244.
4.3.13. 3-(40-N,N-Dimethylaminophenyl)-1-phenyl-3-trimethylsilyl-
1H), 7.95 (d, J¼7.3 Hz, 2H). 13C NMR (125 MHz, CDCl3)
d 0.0 (3C),
oxy-1-propanone (3la). 1H NMR (500 MHz, CDCl3, CHCl3)
d
ꢀ0.04
18.1, 47.1, 70.0, 128.3 (2C), 128.4 (2C), 129.7, 130.0, 130.7, 132.7, 132.9,