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4.5.10. Synthesis of 4-benzyl-1-trimethylsilyloxylbi-
cyclo[3.1.0]hexane (7).20 Following general procedure C;
to a stirred solution of silyl enol ether 4 (2.429 g,
9.87 mmol) in 10 mL dichloromethane, was added diethyl
zinc (30.2 mL, 23.6 mmol). Solution was cooled to 0 8C
using ice bath and neat CH2I2 (3.277 g, 12.2 mmol) was
added dropwise over a period of 15 min, reaction mixture
was brought to rt and stirred for 12 h. Reaction was
monitored by GC and usual workup gave 7 (1.90 g, 74%) as
colorless oil. GC–MS (EI, 70 eV): m/z (%)Z260 (MC, 2),
245 (4), 231 (6), 169 (98), 142 (10), 127 (11), 103 (91), 79
(17), 73 (100).
procedure C; to a stirred solution of silyl enol ether 11
(150 mg, 0.433 mmol) in 2 mL dichloromethane, was added
diethyl zinc (2.2 mL, 1.03 mmol). Solution was cooled to
0 8C using ice bath and neat CH2I2 (211 mg, 0.793 mmol)
was added dropwise over a period of 15 min, reaction
mixture was brought to rt and stirred for 2 days, usual
workup gave 12 (120 mg, 75%) as colorless oil. IR (neat):
yZ2929, 2866, 1715, 1686 cmK1 1H NMR (500 MHz,
.
CDCl3): dZ0.13 (s, 3H), 0.18 (s, 6H), 0.82–0.93 (m, 1H),
1.15–1.35 (m, 2H), 1.68–1.78 (m, 3H), 1.90–1.99 (m, 3H),
2.12 (tt, 2H), 2.20–2.30 (m, 2H) ppm. 13C NMR (125 MHz,
CDCl3): dZ0.90 (Si–(CH3)3), 22.08 (CH2), 22.58 (CH2),
25.00 (CH2), 35.18 (CH2), 33.41 (CH), 33.99 (CH), 38.04
(CH), 69.21 (C), 84.10 (C) ppm. GC–MS (EI, 70 eV): m/z
(%)Z222 (MC, 1), 206 (7), 154 (2), 131 (3), 116 (2), 93 (5),
77 (2), 72 (100).
4.5.11. Synthesis of 4-benzyl-1-trimethylsilyloxylbi-
cyclo[4.1.0]hepane (8). Following general procedure C; to
a stirred solution of silyl enol ether 5 (1.49 g, 5.38 mmol) in
5 mL dichloromethane, was added diethyl zinc (14.4 mL,
11.3 mmol). Solution was cooled to 0 8C using ice bath and
neat CH2I2 (2.821 g, 10.56 mmol) was added dropwise over
a period of 15 min, reaction mixture was brought to rt and
stirred for 12 h and usual workup gave 8 (980 mg, 66%) as
4.5.14. Synthesis of 5-(but-3-enyl)-1-trimethylsilyloxyl-
bicyclo[4.1.0]heptane (14).19 Following general procedure
C; to a stirred solution of silyl enol ether 13 (223 mg,
1 mmol) in 2 mL dichloromethane, was added diethyl zinc
(2.9 mL, 2.32 mmol). Solution was cooled to 0 8C using ice
bath and neat CH2I2 (264 mg, 0.9 mmol) was added
dropwise over a period of 15 min, reaction mixture was
brought to rt and stirred for 2 days, usual workup gave 14
(200 mg, 84%) as a colorless oil. GC–MS (EI, 70 eV): m/z
(%)Z238 (MC, 2), 194 (8), 183 (9), 166 (3), 155 (3), 142
(3), 132 (2), 126 (4), 114 (3), 104 (2), 90 (5), 74 (30), 72
(100), 67 (6), 59 (5), 44 (14).
colorless oil. IR (neat): yZ2928, 2862, 1704, 1453 cmK1
.
1H NMR (500 MHz, CDCl3): dZ0.15 (s, 9H), 0.30 (dd, 1H,
JZ5.6, 5.6 Hz), 0.83–0.89 (m, 1H), 0.90–0.99 (m, 3H),
1.55–1.64 (m, 1H), 1.65–1.75 (m, 2H), 1.84 (ddd, 1H, JZ
5.0, 13.8, 5.6 Hz), 2.18 (dd, 1H, JZ3.7, 13.2 Hz), 2.70 (dd,
1H, JZ7.8, 8.0 Hz), 2.81 (dd, 1H, JZ7.5, 7.5 Hz), 7.19 (dd,
3H, JZ7.5, 7.5 Hz), 7.27 (dd, 2H, JZ8.1, 6.9 Hz) ppm. 13C
NMR (125 MHz, CDCl3): dZ1.40 (CH3), 19.00 (CH2),
21.00 (CH2), 24.29 (CH), 26.88 (CH2), 31.98 (CH2), 39.64
(CH), 44.35 (CH2), 57.41 (C), 125.72 (CH), 128.14 (C),
128.96 (CH), 140.00 (CH) ppm. GC–MS (EI, 70 eV): m/z
(%)Z274 (MC, 1), 259 (3), 246 (5), 245 (2), 231 (9), 185
(10), 184 (60), 183 (100), 169 (11), 156 (15), 155 (26), 142
(13), 130 (17), 129 (9), 93 (13), 91 (25).
4.5.15. Synthesis of 4-(2-phenylethyl)-1-trimethylsilyl-
oxylcyclohex-1-ene (18). Following general procedure C;
to a stirred solution of silyl enol ether 17 (652 mg,
2.525 mmol) in 2.5 mL dichloromethane, was added diethyl
zinc (7.6 mL, 6.04 mmol). Solution was cooled to 0 8C
using ice bath and neat CH2I2 (1.362 g, 5.10 mmol) was
added dropwise over a period of 15 min, reaction mixture
was brought to rt and stirred for 2 days, usual workup gave
18 (545 mg, 36%) as a colorless oil. IR (neat): yZ2920,
4.5.12. Synthesis of 4-benzyl-1-trimethylsilyloxylbi-
cyclo[5.1.0]octane (9). Following general procedure C; to
a stirred solution of silyl enol ether 6 (1.37 g, 5 mmol) in
5 mL dichloromethane, was added diethyl zinc (14.4 mL,
11.3 mmol). Solution was cooled to 0 8C using ice bath and
neat CH2I2 (1.53 g, 5.629 mmol) was added dropwise over a
period of 15 min, reaction mixture was brought to rt and
stirred for 12 h, usual workup gave 9 (1.0 g, 70%) as a
colorless oil. IR (neat): yZ2932, 2368, 2344, 1702,
1
28,235, 1704, 1453 cmK1. H NMR (500 MHz, CDCl3):
dZ0.14 (s, 9H), 0.85–0.86 (m, 1H), 1.10–1.40 (m, 2H),
1.50–1.65 (m, 6H), 1.80–1.90 (m, 1H), 1.96–2.10 (m, 2H),
2.40–2.55 (m, 1H), 2.60–2.70 (m, 1H), 7.16 (dd, 2H, JZ6.2,
7.0 Hz), 7.27 (dd, 2H, JZ7.0, 8.0 Hz) ppm. 13C NMR
(125 MHz, CDCl3): dZ20.48 (CH2), 27.14 (CH2), 29.13
(CH2), 30.48 (CH2), 33.55 (CH2), 34.55 (CH), 34.97 (CH2),
51.00 (C), 125.57 (CH), 125.63 (C), 128.27 (CH), 128.32
(CH) ppm. GC–MS (EI, 70 eV): m/z (%)Z288 (MC, 6),
184 (17), 183 (100), 144 (4), 127 (3), 91 (14), 75 (18).
1456 cmK1 1H NMR (500 MHz, CDCl3): dZ0.05 (s,
.
9H), 0.25 (m, 1H), 0.50–0.70 (m, 1H), 0.94 (dd, 2H, JZ
4.3, 2.5 Hz), 1.03 (dd, 2H, JZ10.6, 10.6 Hz), 1.49–1.60 (m,
2H), 1.63–1.77 (m, 1H), 1.88 (d, 1H, JZ13.8 Hz), 2.10–
2.25 (dm, 2H, JZ14.4 Hz), 2.40 (dd, 1H, JZ8.1, 8.1 Hz),
2.56 (dd, 1H, JZ6.9, 6.9 Hz), 7.15 (ddd, 3H, JZ1.2, 4.3,
6.2 Hz), 7.25 (dd, 2H, JZ7.5, 8.7 Hz) ppm. 13C NMR
(125 MHz, CDCl3): dZ1.20 (CH3), 24.97 (CH), 28.09
(CH2), 31.78 (CH2), 38.34 (CH), 38.86 (CH2), 43.12 (CH2),
44.48 (CH2), 69.65 (C), 125.64 (CH), 128.14 (CH), 129.32
(CH), 141.32 (C) ppm. GC–MS (EI, 70 eV): m/z (%)Z288
(MC, 3), 273 (3), 259 (6), 231 (5), 197 (71), 184 (12), 170
(39), 157 (26), 144 (29), 130 (11), 114 (5), 91 (23), 73 (100).
HRMS: Calcd for C18H28OSi (MC) 288.190944, found
288.190933.
4.5.16. Synthesis of 3-benzyl-1-trimethylsilyloxylbi-
cyclo[5.1.0]oct-2-ene (22). Following general procedure
C; to a stirred solution of silyl enol ether 21 (118 mg,
0.433 mmol) in 2 mL dichloromethane, was added diethyl
zinc (1.3 mL, 1.03 mmol). Solution was cooled to 0 8C
using ice bath and neat CH2I2 (117 mg, 0.438 mmol) was
added dropwise over a period of 15 min, reaction mixture
was brought to rt and stirred for 12 h, usual workup gave 22
(100 mg, 81%) as a colorless oil. IR (neat): yZ2929, 2863,
1706, 1662, 1455, 1376 cmK1 1H NMR (500 MHz,
.
CDCl3): dZ0.19 (dd, 1H, JZ1.8, 5.0 Hz), 0.70–0.77
(m, 1H), 0.78–0.83 (m, 1H), 0.85–0.97 (m, 2H), 1.50–1.68
(m, 1H), 1.74–1.86 (m, 2H), 2.18–2.28 (m, 1H), 3.15 (d, 2H,
4.5.13. Synthesis of 4-(prop-2-ynyl)-1-trimethylsilyl-
oxylbicyclo[4.1.0]heptane (12). Following general