Formation of Some Siloles and Diazasiloles
Hz, 2 H), 5.74 (dd, J ) 19.1, 4.4 Hz, 2 H), 6.03 (dd, J ) 14.7,
4.4 Hz, 2 H), 6.14 (dd, J ) 19.1, 14.3 Hz, 2 H), 7.07-7.13 (m,
4 H). 13C NMR: 8.91 (t), 18.12 (t), 29.33 (t), 125.06 (d), 126.48
(d), 127.94 (d), 129.75 (d), 133.92 (t), 135.32 (d), 137.14 (s),
141.57 (s). 29Si NMR: -15.30. MS: 201 (M + 1+, 19), 200 (38),
173 (19), 172 (100), 159 (48), 158 (21), 146 (25), 145 (42), 144
(32), 131 (22). HR-MS: found 200.1025, calcd C13H16Si 200.1021.
159 (100), 145 (31), 131 (27), 119 (10), 105 (12). HR-MS: found
228.1335, calcd C15H20Si 228.1334.
2-Allyl-2-m e t h yl-1,2,3,4-t e t r a h yd r o-2-sila n a p h t h a -
len e 9d . Yield: 14 mg (6%). Rf (hexane): 0.23. IR: 3078 (w),
2928 (m), 1628 (s), 1484 (m), 1460 (m), 1156 (m), 992 (m), 902
1
(s). H NMR: 0.78-0.83 (m, 2H), 1.59 (dt, J ) 8.1, 1.1 Hz, 4
H), 2.03 (s, 2 H), 2.72-2.77 (m, 2 H), 4.83-4.92 (m, 4 H), 5.66-
5.83 (m, 2 H), 7.04-7.15 (m, 4 H). 13C NMR: 8.09 (t), 16.84
(t), 20.60 (t), 29.60 (t), 113.72 (t), 125.01 (d), 126.48 (d), 127.95
(d), 133.99 (d), 137.36 (s), 141.99 (s). MS: 229 (M + 1+, 20),
187 (36), 186 (18), 160 (22), 159 (53), 146 (19), 145 (100), 133
(13), 131 (25), 119 (10), 105 (12). HR-MS: found 228.1317,
calcd C15H20Si 228.1334.
Alter n a tive Meth od . A solution of 1.2 mmol of Bu3SnH
and 0.1 mmol of AIBN in benzene (10 mL) was slowly added
to a boiling solution of 1 mmol of 4b in 30 mL of benzene via
a syringe pump over 7 h under Ar with stirring. The resulting
mixture was stirred for another 2 h after completion of the
addition. The solvent was removed completely. The residue
was dissolved in diethyl ether (30 mL) and stirred with 10%
KF (aq) (20 mL) for 4 h. After filtering off the white precipitate,
the filtrate was extracted with diethyl ether, and the combined
organic phases were dried over anhydrous MgSO4. After
evaporation of the solvent, the crude product was purified by
flash chromatography and preparative GC [8b, 100 mg (50%);
9b, 50 mg (25%)].
6-Allyl-6-vin yl-6,7,8,9-tetr a h yd r o-5H-6-sila ben zocyclo-
h ep ta n e 11. Yield: 41 mg (18%). Rf (hexane): 0.23. IR: 3060
(w), 3005 (m), 2920 (s), 2860 (m), 1660 (m), 1600 (w), 1490
(m), 1455 (m), 1405 (m), 1200 (s), 1180 (m), 1150 (s), 1005 (m),
1
955 (m). H NMR: 0.82 (t, J ) 7.0 Hz, 2 H), 1.53 (dt, J ) 3.7,
1.1 Hz, 1 H), 1.56 (dt, J ) 3.7, 1.1 Hz, 1 H), 1.73-1.95 (m, 2
H), 2.27 (d, J ) 14.0 Hz, 1 H), 2.34 (d, J ) 14.0 Hz, 1 H), 2.72-
(t, J ) 5.9 Hz, 2 H), 4.83-4.90 (m, 2 H), 5.66-5.81 (m, 2 H),
5.98-6.11 (m, 2 H), 7.02-7.08 (m, 4 H). 13C NMR: 12.81 (t),
20.56 (t), 21.93 (t), 23.84 (t), 35.06 (t), 113.52 (t), 125.07 (d),
126.27 (d), 129.13 (d), 129.55 (d), 133.29 (t), 134.13 (d), 135.56
(d), 138.60 (s), 141.17 (s). 29Si NMR: -13.861. MS: 228 (M+,
25), 188 (25), 187 (100), 160 (12), 159 (54), 145 (24), 131 (25),
105 (11). HR-MS: found 228.1333, calcd C15H20Si 228.1334.
Ra d ica l Rea ction of 4c: 2-Allyl-1,2-d im eth yl-2,3-d ih y-
d r o-1H-ben zo[c]silole 8c. Purified by GC. Yield: 81 mg
(40%) as colorless oil (6:1 mixture of stereoisomers). Rf (hex-
ane): 0.36. IR: 3060 (w), 3005 (w), 2960 (w), 1660 (m), 1630
1
(m), 1470 (w), 1250 (m), 1200 (s), 1150 (m), 990 (m). H NMR:
0.15 (s, 3 H), 1.30 (d, J ) 7.7 Hz, 3 H), 1.74 (d, J ) 8.1 Hz, 2
H), 2.00 (d, J ) 17.6 Hz, 1 H), 2.08 (d, J ) 17.3 Hz, 1 H), 2.28
(q, J ) 7.7 Hz, 1 H), 4.85-4.96 (m, 2 H), 5.76-5.90 (m, 1 H),
7.07-7.18 (m, 2 H), 7.18-7.25 (m, 2 H). 13C NMR: -7.61 (q),
15.57 (q), 17.96 (t), 21.69 (t), 23.74 (d), 113.53 (t), 125.65 (d),
125.91 (d), 126.82 (d), 129.12 (d), 134.22 (d), 140.90 (s), 147.61
(s). 29Si NMR: 21.259. MS: 202 (M+, 13), 162 (12), 161 (60),
160 (100), 159 (18), 145 (33), 133 (24), 115 (10), HR-MS: found
202.1180, calcd C13H18Si 202.1178.
Be n zyld ia llyl-(2-t r ib u t ylst a n n yle t h yl)sila n e
12.
Yield: 10 mg (2%). Rf (hexane): 0.31. IR: 3060 (w), 2920 (m),
1640 (w), 1600 (m), 1155 (s), 1010 (m), 990 (m), 900 (s). 1H
NMR: 0.79-0.84 (m, 5 H), 0.88-0.93 (m, 12 H), 1.25-1.37
(m, 8 H), 1.42-1.53 (m, 6 H), 1.59 (d, J ) 8.1 Hz, 4 H), 2.17 (s,
2 H), 4.85-4.93 (m, 4 H), 5.70-5.84 (m, 2 H), 7.03-7.11 (m, 3
H), 7.19-7.25 (m, 2 H). 13C NMR: 0.065 (t), 7.34 (t), 8.61 (t),
13.74 (q), 19.07 (t), 21.20 (t), 27.42 (t), 29.27 (t), 113.55 (t),
124.09 (d), 128.24 (d), 128.27 (d), 134.50 (d), 139.78 (s). MS:
520 (M + 1+, 5), 518 (M - 1+, 4), 468 (20), 466 (33), 464 (100),
462 (90), 460 (49), 235 (10), 177 (12), 119 (9).
2-Allyl-2-m e t h yl-1,2,3,4-t e t r a h yd r o-2-sila n a p h t h a -
len e 9c. Purified by GC. Yield: 6 mg (8%) as colorless oil. Rf
(hexane): 0.36. IR: 2930 (m), 2850 (m), 1630 (m), 1485 (m),
1465 (m), 1250 (m), 1150 (s), 1070 (m), 1035 (s). 1H NMR:
0.049 (s, 3 H), 0.65-0.75 (m, 1 H), 0.80-0.90 (m, 1 H), 1.56
(d, J ) 8.0 Hz, 2 H), 1.93 (d, J ) 14.3 Hz, 1 H), 2.06 (d, J )
14.3 Hz, 1 H), 2.75 (t, J ) 6.6 Hz, 2 H), 4.82-4.91 (m, 2 H),
5.70-5.85 (m, 1 H), 7.05-7.13 (m, 4 H). 13C NMR: -4.14 (q),
9.87 (t), 18.82 (t), 22.48 (t), 29.57 (t), 113.29 (t), 124.90 (d),
126.36 (d), 127.89 (d), 129.65 (d), 134.39 (d), 137.78 (s), 141.57
(s). MS: 202 (M+, 84), 188 (25), 162 (44), 161 (100), 160 (82),
159 (40), 145 (63), 133 (44), 131 (22), 115 (18). HR-MS: found
202.1176, calcd C13H18Si 202.1178.
Ben zyld ia llylvin ylsila n e 13. Yield: 11 mg (5%). Rf (hex-
ane): 0.28. IR: 3080 (m), 3028 (s), 2924 (m), 1630 (s), 1600
(m), 1494 (s), 1452 (m), 1460 (s), 1262 (m), 1160 (s), 1008 (m),
1
958 (m), 932 (m). H NMR: 1.62-1.66 (m, 4 H), 2.23 (s, 2 H),
4.89-4.95 (m, 4 H), 5.67-5.84 (m, 3 H), 6.04-6.09 (m, 2 H),
7.04-7.12 (m, 3 H), 7.21-7.26 (m, 2 H). 13C NMR: 19.37 (t),
21.80 (t), 114.18 (t), 124.29 (d), 128.24 (d), 128.51 (d), 133.87
(d), 134.17 (t), 134.32 (d), 139.01 (s). MS: 228 (M+, 15), 188
(32), 187 (100), 159 (30), 146 (25), 145 (98), 137 (55), 132 (24),
119 (20), 109 (27).
6-Meth yl-6-vin yl-6,7,8,9-tetr a h yd r o-5H-6-sila ben zocy-
cloh ep ta n e 10. Yield: 51 mg (25%). Rf (hexane): 0.42. IR:
3050 (w), 2930 (s), 2860 (s), 1630 (w), 1590 (w), 1450 (m), 1405
o-Vin ylben zyld ia llylsila n e 14. Yield: 9 mg (4%). Rf
(hexane): 0.23. IR: 3080 (m), 2924 (m), 2130 (s), 1630 (s), 1482
(m), 1448 (w), 1418 (m), 1262 (w), 1160 (s), 992 (m), 902 (s).
1H NMR: 1.62-1.66 (m, 4 H), 2.29 (d, J ) 3.7 Hz, 2 H), 3.84
(m, 1 H), 4.89-4.97 (m, 4 H), 5.29 (dd, J ) 10.7, 1.5 Hz, 1 H),
5.63 (dd, J ) 17.3, 1.5 Hz, 1 H), 5.69-5.84 (m, 2 H), 6.93 (dd,
J ) 17.3, 10.7 Hz, 1 H), 7.03-7.19 (m, 3 H), 7.46-7.49 (m, 1
H). 13C NMR: 17.69 (t), 18.23 (t), 114.30 (t), 115.22 (t), 125.02
(d), 125.96 (d), 127.77 (d), 129.44 (d), 133.98 (d), 135.12 (d),
135.65 (s), 137.04 (s). MS: 229 (M + 1+, 12), 187 (18), 186 (20),
159 (65), 146 (30), 145 (100), 143 (19), 131 (30), 119 (12), 105
(10). HR-MS: found 228.1334, calcd C15H20Si+ 228.1334.
Ra d ica l Rea ction of 4e: 2,2-Dim eth yl-1-tr im eth ylsi-
lylm eth ylen e-2,3-d ih yd r o-1H-ben zo[c]silole 15. Yield: 221
mg (90%). Rf (hexane): 0.38. IR: 3060 (m), 3005 (m), 2960 (s),
2900 (m), 1690 (m), 1550 (m), 1470 (s), 1450 (m), 1395 (m),
1295 (m), 1250 (s), 1205 (s), 1150 (m), 1130 (s), 1065 (m), 940
(m). 1H NMR: 0.27 (s, 9 H), 0.41 (s, 6 H), 2.10 (s, 2 H), 7.14 (s,
1 H), 7.18-7.23 (m, 2 H), 7.29-7.32 (m, 1 H), 7.59-7.65 (m, 1
H). 13C NMR: -1.12 (q), 0.32 (q), 19.76 (t), 120.91 (d), 125.89
(d), 128.05 (d), 130.36 (d), 137.37 (d), 142.34 (s), 145.02 (s),
158.72 (s). NOE: irradiation of the vinylic H led to an
enhanced signal of the adjacent aromatic (ortho) C-H and vice
versa. 29Si NMR: -8.313, 5.941. MS: 247 (M + 1+, 28), 246
1
(s), 1250 (m), 1150 (s), 1065 (m), 1005 (m), 955 (m). H NMR:
-0.0078 (s, 3 H), 0.72-0.90 (m, 2 H), 1.69-1.82 (m, 1 H), 1.85-
1.98 (m, 1 H), 2.19 (d, J ) 14.0 Hz, 1 H), 2.36 (d, J ) 14.0 Hz,
1 H), 2.71-2.75 (m, 2 H), 5.70 (dd, J ) 19.5, 4.8 Hz, 1 H), 5.96
(dd, J ) 14.7, 4.8 Hz, 1 H), 6.09 (dd, J ) 19.5, 14.7 Hz, 1 H),
7.00-7.11 (m, 4 H). 13C NMR: -5.03 (q), 15.18 (t), 23.90 (t),
24.08 (t), 35.24 (t), 124.90 (d), 126.22 (d), 128.94 (d), 129.55
(d), 132.27 (t), 137.52 (d), 139.13 (s), 141.32 (s). 29Si NMR:
-12.367. MS: 203 (M + 1+, 14), 202 (M+, 63), 187 (15), 174
(20), 162 (21), 161 (100), 159 (52), 146 (33), 145 (30), 131 (21).
HR-MS: found 202.1176, calcd C13H18Si 202.1178.
Ra d ica l Rea ction of 4d : 1,2-Dia llyl-2,3-d ih yd r o-1H-
ben zo[c]silole 8d . Yield: 66 mg (29%). Rf (hexane): 0.23.
IR: 3080 (m), 2958 (m), 1672 (m), 1630 (s), 1472 (m), 1392
1
(m), 1260 (w), 1160 (s), 992 (m), 902 (s). H NMR: 1.35 (d, J
) 7.7 Hz, 3 H), 1.70-1.81 (m, 4 H), 2.06 (d, J ) 5.2 Hz, 2 H),
2.35 (d, J ) 7.7 Hz, 1 H), 4.86-4.98 (m, 4 H), 5.76-5.88 (m, 2
H), 7.07-7.24 (m, 4 H). 13C NMR: 15.44 (q), 16.22 (t), 17.56
(t), 19.60 (t), 23.65 (d), 113.97 (t), 114.11 (t), 125.74 (d), 125.98
(d), 126.59 (d), 129.08 (d), 133.80 (d), 133.87 (d), 140.51 (s),
147.31 (s). MS: 229 (M + 1+, 14), 187 (22), 186 (40), 160 (22),
J . Org. Chem, Vol. 67, No. 25, 2002 8909