844 J. Chin. Chem. Soc., Vol. 51, No. 4, 2004
Lee et al.
(CH), 56.33 (C), 36.85 (CH), 28.35 (CH), -1.19 (CH3); MS
m/z (%): 179 ((M-Cl)+, 25); HRMS calcd. for C10H15OSi m/z
179.0892, found 179.0886.
to give benzaldehyde (1.99 g, 94%).
Reaction of 2-chloro-3-trimethylsilyl-8-oxatricyclo-
[3.2.1.02,4]oct-6-ene (18) with tetrabutylammonium fluo-
ride by VGSR
Diels-Alder reaction of 2-chloro-3-trimethylsilyl-8-oxa-
tricyclo[3.2.1.02,4]oct-6-ene (17) and DPIBF
2-Chloro-3-trimethylsilyl-8-oxatricyclo[3.2.1.02,4]oct-
6-ene (18) (4.30 g, 20.00 mmol) was passed through the col-
umn containing the solid tetrabutylammonium fluoride at
room temperature. After the product had been collected onto
the walls of a cold trap at -196 °C, the mixture was warmed up
to room temperature. The reaction mixture was fractionated
to give benzaldehyde (1.95 g, 92%).
Compound 17 (4.30 g, 20.00 mmol) and diphenyliso-
benzofuran (5.94 g, 22.00 mmol) were dissolved in 20 mL of
dry tetrahydrofuran. The mixture was refluxed for 6 h and
then concentrated and chromatographed (hexane:CH2Cl2 =
5:1) to give colorless solid 19 (5.70 g, 59%, Rf = 0.15) and 20
(3.45 g, 36%, Rf = 0.26). Compound 19: mp 166-168 °C; IR
(neat): 3056, 3034, 2956, 2924, 2853, 1604, 1498, 1448,
1365, 1335, 1250, 991, 839, 762, 696 cm-1; 1H NMR (CDCl3)
d 7.73-7.67 (m, 4H), 7.54-7.43 (m, 6H), 7.20-7.17 (m, 2H),
6.95-6.87 (m, 2H), 4.07 (d, 1H, J = 8.3 Hz), 4.05 (s, 1H), 3.99
(s, 1H), 3.33 (d, 1H, J = 8.3 Hz), 1.31 (d, 1H, J = 6.0 Hz), 0.80
(d, 1H, J = 6.0 Hz), 0.08 (s, 9H); 13C NMR (CDCl3) d 147.04
(C), 146.59 (C), 138.80 (C), 138.56 (C), 128.60 (CH), 128.57
(CH), 128.31 (CH), 128.15 (CH), 127.16 (CH), 127.05 (CH),
126.99 (CH), 126.36 (CH), 119.51 (CH), 119.23 (CH), 89.15
(C), 88.88 (C), 78.66 (CH), 76.44 (CH), 57.30 (CH), 54.63
(CH), 52.17 (C), 29.72 (CH), 11.61 (CH), -1.11 (CH3); MS
m/z (%): 484 (M+, 6); HRMS calcd. for C30H29O2ClSi m/z
484.1625, found 484.1623. Compound 20: mp 292-293 °C;
IR (neat): 3056, 3022, 2989, 2956, 2889, 1602, 1498, 1454,
6,7-Benzo-2-chloro-3-trimethylsilyl-1,5-diphenyl-8-oxatri-
cyclo[3.2.1.02,4]oct-6-ene (30)
1-Bromo-2,2-dichloro-3-trimethylsilylcyclopropane
(4.40 g, 16.80 mmol) and diphenylisobenzofuran (5.00 g,
18.50 mmol) were dissolved in 15 mL of dry tetrahydrofuran.
Methyllithium (1.5 M in ether, 17.00 mL) was added drop-
wise. The mixture was stirred at room temperature for 4 h.
Cool the mixture to room temperature and then remove the
tetrahydrofuran under reduced pressure and the residue was
chromatographed (hexanes:CH2Cl2 = 5:1) to yield white
powder 30 (4.42 g, 95%, Rf = 0.28). Compound 30: mp
148-151 °C; IR (neat): 3070, 2958, 1608, 1450, 1242, 1190,
1024, 979, 930, 836, 748, 700 cm-1; H NMR (CDCl3) d
1
1
1347, 1306, 1247, 1030, 993, 864, 839, 746, 701 cm-1; H
7.80-7.77 (m, 2H), 7.61-7.58 (m, 2H), 7.49-7.42 (m, 6H),
7.28-7.24 (m, 3H), 7.10-7.11 (m, 1H), 2.10 (d, 1H, J = 6.2
Hz), 1.95 (d, 1H, J = 6.2 Hz), 0.24 (s, 9H); 13C NMR (CDCl3)
d 149.87 (C), 148.14 (C), 135.59 (C), 133.52 (C), 129.45
(CH), 129.12 (CH), 128.90 (CH), 128.57 (CH), 128.07 (CH),
126.90 (CH), 126.35 (CH), 122.87 (CH), 119.93 (CH), 91.60
(C), 88.89 (C), 57.76 (C), 36.12 (CH), 24.61 (CH), -1.03
(CH3). Anal. Calcd. for C26H25OClSi, C, 74.88; H, 6.04.
Found: C, 74.86; H, 5.90. MS m/z (%): 628 (M+, 0.15);
HRMS calcd. for C26H25OClSi m/z 416.1363, found 416.1354.
NMR (CDCl3) d 7.76-7.42 (m, 4H), 7.57-7.51 (m, 4H),
7.44-7.40 (m, 2H), 7.16-7.08 (m, 4H), 4.14 (s, 1H), 4.00 (s,
1H), 3.50 (d, 1H, J = 6.5 Hz), 2.86 (d, 1H, J = 6.5 Hz), 1.19 (d,
1H, J = 5.8 Hz), 0.63 (d, 1H, J = 5.8 Hz), 0.42 (s, 9H); 13C
NMR (CDCl3) d 149.35 (C), 148.87 (C), 137.06 (C), 136.90
(C), 128.72 (CH), 127.66 (CH), 126.85 (CH), 126.76 (CH),
126.24 (CH), 126.06 (CH), 118.71 (CH), 118.55 (CH), 89.83
(C), 89.68 (C), 79.77 (CH), 77.52 (CH), 57.08 (CH), 54.91
(CH), 51.53 (C), 28.49 (CH), 9.11 (CH), -1.06 (CH3); MS m/z
(%): 484 (M+, 2); HRMS calcd. for C30H29O2ClSi m/z
484.1625, found 484.1621.
Phenyl-(4-phenyl-[1]naphthyl)ketone (31)
6,7-Benzo-2-chloro-3-trimethylsilyl-1,5-diphenyl-8-
oxatricyclo[3.2.1.02,4]oct-6-ene (30) (0.5 g, 1.2 mmol) and
n-Bu4NF (1.0 M in THF, 0.35 mL, 1.32 mmol) were dissolved
in 5 mL of dry tetrahydrofuran and refluxed for 24 h. Cool the
mixture to room temperature and wash it with water and
brine. The residue was chromatographed (10% EA/Hexanes)
to yield white powder 31 (0.26 g, 70%, Rf = 0.23). Compound
31: 1H NMR (CDCl3) d 8.20-8.18 (m, 1H), 8.00-7.94 (m, 3H),
7.64-7.45 (m, 12H); 13C NMR (CDCl3) d 198.06 (C), 143.58
(C), 140.26 (C), 138.45 (C), 135.91 (C), 133.31 (CH), 132.12
Reaction of 2-chloro-3-trimethylsilyl-8-oxatricyclo-
[3.2.1.02,4]oct-6-ene (17) with tetrabutylammonium fluo-
ride by VGSR
2-Chloro-3-trimethylsilyl-8-oxatricyclo[3.2.1.02,4]oct-
6-ene (17) (4.30 g, 20.00 mmol) was passed through the col-
umn containing the solid tetrabutylammonium fluoride at
room temperature. After the product had been collected onto
the walls of a cold trap at -196 °C, the mixture was warmed up
to room temperature. The reaction mixture was fractionated