R. Riveiros, L. Saya, J. Pérez Sestelo, L. A. Sarandeses
FULL PAPER
ethynyl)indium (0.39 mmol) afforded 13 [155 mg, 81%, (E)/(Z) =
with tris[(trimethylsilyl)ethynyl]indium (0.90 mmol) afforded 20
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97:3]. 1H NMR (300 MHz, CDCl3, 25 °C): δ = 0.91 (t, J = 7.2 Hz, (288 mg, 90%). H NMR (300 MHz, CDCl3, 25 °C): δ = 0.20 (s, 9
3 H), 1.35–1.49 (m, 6 H), 2.41 (q, J = 8.3 Hz, 2 H), 5.68 (d, J = H), 0.22 (s, 9 H), 0.89 (t, J = 7.4 Hz, 3 H), 1.19–1.42 (m, 10 H),
10.8 Hz, 1 H), 5.99 (dt, J = 10.8, 7.4 Hz, 1 H), 7.28–7.34 (m, 2 H),
7.41–7.46 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ =
2.34 (q, J = 7.4 Hz, 2 H), 6.42 (t, J = 7.4 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = –0.1 (6ϫ CH3), 14.1 (CH3), 22.6
14.1 (CH3) 22.5 (CH2), 28.6 (CH2), 30.4 (CH2), 31.5 (CH2), 87.5 (CH2), 28.3 (CH2), 29.0 (CH2), 29.2 (CH2), 30.8 (CH2), 31.8 (CH2),
(C), 93.0 (C), 109.0 (CH), 123.8 (C), 128.3 (2ϫ CH), 131.4 (2ϫ 91.4 (C), 98.3 (C), 99.8 (C), 102.5 (C), 105.8 (C), 152.2 (CH) ppm.
CH), 144.5 (CH) ppm. MS (EI): m/z (%) = 202 (5) [M]+, 129 (100) MS (EI): m/z (%) = 318 (8) [M]+, 303 (13) [M – CH3]+, 105 (100).
[M – C5H11]+. GC [120 °C (2 min) up to 200 °C at 10 °C/min]: tR HRMS (EI): calcd. for C19H34Si2 318.2194; found 318.2192.
= 4.6 min.
[(Z)-1-Bromonon-1-enyl]benzene (22): According to procedure B,
the reaction of 15 (284 mg, 1.000 mmol) with triphenylindium
Trimethyl[(E)-non-3-en-1-ynyl]silane (14):[34] According to the gene-
ral procedure, the reaction of 2 (224 mg, 1.000 mmol) with tris[(tri-
methylsilyl)ethynyl]indium (0.40 mmol) afforded 14 [167 mg, 86%,
(0.40 mmol) afforded 22 (155 mg, 55%). 1H NMR (300 MHz,
CDCl3, 25 °C): δ = 0.91 (t, J = 6.6 Hz, 3 H), 1.28–1.55 (m, 10 H),
2.38 (q, J = 7.1 Hz, 2 H), 6.22 (t, J = 7.1 Hz, 1 H), 7.26–7.37 (m,
3 H), 7.52–7.55 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C):
δ = 14.1 (CH3), 22.6 (CH2), 28.4 (CH2), 29.1 (CH2), 29.3 (CH2),
31.8 (CH2), 32.5 (CH2), 125.2 (C), 127.5 (2ϫ CH), 128.2 (3ϫ CH),
132.0 (CH), 140.2 (C) ppm. MS (EI): m/z (%) = 282 (12) [M]+
(81Br), 280 (13) [M]+ (79Br), 105 (100). HRMS (EI): calcd. for
C15H21Br 280.0821; found 280.0826.
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(E)/(Z) = 97:3]. H NMR (300 MHz, CDCl3, 25 °C): δ = 0.20 (s, 9
H), 0.89 (t, J = 6.8 Hz, 3 H), 1.24–1.44 (m, 6 H), 2.10 (q, J =
7.1 Hz, 2 H), 5.47–5.52 (m, 1 H), 6.22–6.27 (m, 1 H) ppm. 13C
NMR (75 MHz, CDCl3, 25 °C): δ = 0.1 (3ϫ CH3), 14.1 (CH3),
22.5 (CH2), 28.4 (CH2), 31.3 (CH2), 33.1 (CH2), 92.5 (C), 104.3
(C), 109.6 (CH), 146.5 (CH) ppm. MS (EI): m/z (%) = 194 (10)
[M]+, 73 (100). GC (200 °C): tR = 4.9 min.
1,1-Diphenylnon-1-ene (16):[35] According to procedure A, the reac-
tion of 15 (280 mg, 0.986 mmol) with triphenylindium (0.89 mmol)
afforded 16 (198 mg, 72%). 1H NMR (300 MHz, CDCl3, 25 °C): δ
= 0.90 (t, J = 6.9 Hz, 3 H), 1.27–1.54 (m, 10 H), 2.13 (q, J = 7.4 Hz,
2 H), 6.11 (t, J = 7.4 Hz, 1 H), 7.12–7.50 (m, 10 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 14.1 (CH3), 22.6 (CH2), 29.1 (CH2),
29.2 (CH2), 29.7 (CH2), 30.0 (CH2), 31.8 (CH2), 126.7 (CH), 126.8
(CH), 127.2 (2ϫ CH), 128.04 (2ϫ CH), 128.08 (2ϫ CH), 130.0
(2ϫ CH), 130.4 (CH), 140.4 (C), 141.4 (C), 142.9 (C) ppm. MS
(EI): m/z (%) = 278 (37) [M]+, 193 (100).
2-Methyldec-2-ene (17):[36] According to procedure A, the reaction
of 15 (289 mg, 1.018 mmol) with trimethylindium (0.92 mmol) af-
forded 17 (124 mg, 79%). 1H NMR (200 MHz, CDCl3, 25 °C): δ =
0.89 (t, J = 5.9 Hz, 3 H), 1.18–1.25 (m, 10 H), 1.60 (s, 3 H), 1.69
(s, 3 H), 1.97 (m, 2 H), 5.12 (t, J = 14.2 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 14.4 (CH3), 17.8 (CH3), 22.7 (CH2),
25.8 (CH3), 28.2 (CH2), 29.9 (CH2), 30.5 (CH2), 31.7 (CH2), 31.8
(CH2), 125.1 (CH), 131.2 (C) ppm.
5-Butyltridec-5-ene (18):[37] According to procedure A, the reaction
of 15 (287 mg, 1.011 mmol) with tri-n-butylindium (0.91 mmol) af-
forded 18 (202 mg, 84%). 1H NMR (200 MHz, CDCl3, 25 °C): δ =
0.89 (m, 9 H), 1.33 (m, 18 H), 1.93–2.00 (m, 6 H), 5.10 (t, J =
13.6 Hz,1 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 13.76
(CH3), 13.79 (2ϫ CH3), 22.3 (CH2), 22.4 (CH2), 22.6 (CH2), 27.4
(CH2), 29.0 (CH2), 29.1 (CH2), 29.5 (CH2), 29.9 (CH2), 30.3 (CH2),
30.5 (CH2), 31.6 (CH2), 36.4 (CH2), 124.5 (CH), 139.3 (C) ppm.
MS (EI): m/z (%) = 238 (20) [M]+, 69 (100).
[(Z)-3-Bromoundec-3-en-1-ynyl]trimethylsilane (23): According to
procedure B, the reaction of 15 (280 mg, 0.986 mmol) with tris[(tri-
methylsilyl)ethynyl]indium (0.40 mmol) afforded 23 (226 mg, 76%).
1H NMR (300 MHz, CDCl3, 25 °C): δ = 0.21 (s, 9 H), 0.89 (t, J =
6.6 Hz, 3 H), 1.21–1.56 (m, 10 H), 2.21 (q, J = 7.1 Hz, 2 H), 6.34
(t, J = 7.1 Hz, 1 H) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ =
–0.3 (3ϫ CH3), 14.1 (CH3), 22.6 (CH2), 27.9 (CH2), 29.0 (CH2),
29.2 (CH2), 31.7 (CH2), 32.0 (CH2), 94.5 (C), 102.2 (C), 102.4 (C),
141.5 (CH) ppm. MS (EI): m/z (%) = 299 (1) [M – H]+ (79Br), 125
(100). HRMS (EI): calcd. for C14H25SiBr 300.0903; found
300.0907.
[(Z)-3-Bromoundec-3-en-1-ynyl]benzene (24): According to pro-
cedure B, the reaction of 15 (280 mg, 0.986 mmol) with tris(phenyl-
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ethynyl)indium (0.40 mmol) afforded 24 (211 mg, 70%). H NMR
(300 MHz, CDCl3, 25 °C): δ = 0.93 (t, J = 7.1 Hz, 3 H), 1.21–1.52
(m, 10 H), 2.30 (q, J = 7.1 Hz, 2 H), 6.39 (t, J = 7.1 Hz, 1 H),
7.33–7.37 (m, 3 H), 7.45–7.50 (m, 2 H) ppm. 13C NMR (75 MHz,
CDCl3, 25 °C): δ = 14.1 (CH3), 22.6 (CH2), 28.0 (CH2), 29.1 (CH2),
29.2 (CH2), 31.7 (CH2), 32.1 (CH2), 87.7 (C), 88.9 (C), 102.4 (C),
122.2 (C), 128.3 (2ϫ CH), 128.7 (CH), 131.6 (2ϫ CH), 140.6 (CH)
ppm. MS (EI): m/z (%) = 306 (10) [M]+ (81Br), 304 (10) [M]+ (79Br),
129 (100). HRMS (EI): calcd. for C17H21Br 304.0821; found
304.0824.
1,1Ј-[(Z)-1-Bromoethene-1,2-diyl]bisbenzene (25):[15] According to
procedure B, the reaction of 21 (261 mg, 0.997 mmol) with tri-
phenylindium (0.40 mmol) afforded 25 (147 mg, 57%). 1H NMR
(300 MHz, CDCl3, 25 °C): δ = 7.35–7.80 (m, 11 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 124.1 (C), 127.8 (2ϫ CH), 128.0
(CH), 128.2 (2ϫ CH), 128.3 (2ϫ CH), 128.7 (CH), 129.2 (2ϫ CH),
129.9 (CH), 136.3 (C), 141.0 (C) ppm. MS (EI): m/z (%) = 260 (20)
[M]+ (81Br), 258 (21) [M]+ (79Br), 178 (100) [M – HBr]+. HRMS
(EI): calcd. for C14H11Br 258.0039; found 258.0041.
[3-(Phenylethynyl)undec-3-en-1-ynyl]benzene (19): According to
procedure A, the reaction of 15 (280 mg, 0.986 mmol) with tris-
(phenylethynyl)indium (0.90 mmol) afforded 19 (235 mg, 73%). 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 0.91 (t, J = 6.9 Hz, 3 H),
1.29–1.55 (m, 10 H), 2.49 (q, J = 7.4 Hz, 2 H), 6.50 (t, J = 7.7 Hz,
1 H), 7.31–7.40 (m, 6 H), 7.49–7.55 (m, 4 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 14.1 (CH3), 22.6 (CH2), 28.6 (CH2),
29.1 (CH2), 29.2 (CH2), 31.0 (CH2), 31.8 (CH2), 84.9 (C), 86.5 (C),
87.5 (C), 92.8 (C), 105.6 (C), 123.07 (C), 123.09 (C), 128.20 (CH),
128.24 (2ϫ CH), 128.28 (2ϫ CH), 128.4 (CH), 131.60 (2ϫ CH),
131.62 (2ϫ CH), 149.7 (CH) ppm. MS (EI): m/z (%) = 326 (14)
[M]+, 255 (15) [M – C5H11]+, 115 (100). HRMS (EI): calcd. for
C25H26 326.2029; found 326.2030.
[(Z)-2-Bromobuta-1,3-dienyl]benzene (26):[38] According to pro-
cedure B, the reaction of 21 (260 mg, 0.993 mmol) with trivinyl-
indium (0.40 mmol) afforded 26 (143 mg, 69%). 1H NMR
(300 MHz, CDCl3, 25 °C): δ = 5.35 (d, J = 10.4 Hz, 1 H), 5.75 (d,
J = 16.2 Hz, 1 H), 6.53 (dd, J = 16.2, 10.4 Hz, 1 H), 7.00 (s, 1 H),
7.30–7.42 (m, 3 H), 7.71 (d, J = 7.1 Hz, 2 H) ppm. 13C NMR
(75 MHz, CDCl3, 25 °C): δ = 119.0 (CH2), 123.9 (C), 128.1 (2ϫ
CH), 128.3 (CH), 129.5 (2ϫ CH), 132.3 (CH), 135.6 (C), 137.1
(CH) ppm. MS (EI): m/z (%) = 209 (6) [M]+ (81Br), 207 (6) [M]+
Trimethyl{3-[(trimethylsilyl)ethynyl]undec-3-en-1-ynyl}silane (20):
According to procedure A, the reaction of 15 (285 mg, 1.004 mmol)
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Eur. J. Org. Chem. 2008, 1959–1966