J.-c. Shi, E.-i. Negishi / Journal of Organometallic Chemistry 687 (2003) 518ꢀ
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524
523
4.3.7. (1Z, 3S)-1-Bromo-3-methyl-1-(2’-thienyl)-1-
pentene
4.4.1. (2E)-2-Phenyl-2-nonene [14]
Yield, 92%. Stereoisomeric purity, ]
(300 MHz, CDCl3) d 0.95 (t, Jꢃ6.4 Hz, 3H), 1.3ꢀ
(m, 8H), 2.08 (s, 3H), 2.2ꢀ2.3 (m, 2H), 5.84 (t, Jꢃ
Hz, 1H), 7.25ꢀ
7.45 (m, 5H). 13C-NMR (75 MHz,
CDCl3) d 14.10, 15.73, 22.67, 28.80, 29.09, 29.59,
31.82, 125.58 (2C), 126.38, 128.10 (2C), 128.82, 134.44,
144.06.
1
/
98%. H-NMR
1.55
6.1
Yield, 86%. Stereoisomeric purity, ]
/
98%. [a]2D3
ꢁ
/
/
/
1
39.2 (c 5.3, CHCl3). H-NMR (300 MHz, CDCl3) d
0.92 (t, Jꢃ6.3 Hz, 3H), 1.05 (d, Jꢃ6.7 Hz, 3H), 1.35ꢀ
1.5 (m, 2H), 2.6ꢀ2.75 (m, 1H), 6.04 (d, Jꢃ9.0 Hz, 1H),
6.9ꢀ7.0 (m, 1H), 7.1ꢀ
7.25 (m, 2H). 13C-NMR (75 MHz,
/
/
/
/
/
/
/
/
/
/
CDCl3) d 12.20, 19.73, 29.88, 38.96, 116.30, 125.29,
126.92, 127.27, 136.26, 143.67. MS (CI) m/z (%) 245 (22)
[Mꢁꢁ
243.9922.
/
1]. HRMS Calc. for C10H13Br 243.9921, Found
4.4.2. (3E)-3-Phenyl-3-decene
1
Yield, 95%. Stereoisomeric purity, ]
(300 MHz, CDCl3) d 0.92 (t, Jꢃ
Jꢃ7.5 Hz, 3H), 1.2ꢀ1.5 (m, 8H), 2.15ꢀ
2.45ꢀ2.6 (m, 2H), 5.66 (t, Jꢃ7.3 Hz, 1H), 7.25ꢀ
/
98%. H-NMR
/
6.1 Hz, 3H), 1.00 (t,
2.25 (m, 2H),
7.4 (m,
/
/
/
4.3.8. (1Z, 3S)-1-Bromo-3-methyl-1-(2’-thiazolyl)-1-
penene
/
/
/
5H). 13C-NMR (75 MHz, CDCl3) d 13.59, 14.09, 22.67,
22.88, 28.43, 29.12, 29.90, 31.82, 126.27 (2C), 126.35,
128.11 (2C), 128.52, 141.38, 143.18. IR (neat) 3055,
2927, 2855, 1598, 1490, 1466, 1120 cmꢄ1. MS (CI) m/z
Yield, 82%. Stereoisomeric purity, ]
/
98%. [a]2D3
ꢁ
/
1
32.5 (c 3.5, CHCl3). H-NMR (300 MHz, CDCl3) d
0.94 (t, Jꢃ7.5 Hz, 3H), 1.10 (d, Jꢃ6.7 Hz, 3H), 1.45ꢀ
1.55 (m, 2H), 2.65ꢀ2.8 (m, 1H), 6.88 (d, Jꢃ9.3 Hz, 1H),
7.30 (d, Jꢃ3.2 Hz, 1H), 7.82 (d, Jꢃ
3.2 Hz, 1H). 13C-
/
/
/
/
/
(%) 217 (100) [Mꢁꢁ
1]. HRMS Calc. for C16H24
/
/
/
216.1878, Found 216.1883.
NMR (75 MHz, CDCl3) d 11.75, 18.97, 29.18, 38.46,
115.17, 119.72, 140.21, 143.67, 167.73. IR (neat) 3060,
2926, 1595, 1480, 1456, 1130 cmꢄ1. MS (CI) m/z (%)
4.4.3. (5E)-5-Phenyl-5-dodecene
1
247 (100) [Mꢁꢁ
1]. HRMS Calc. for C9H12BrNS
/
Yield, 95%. Stereoisomeric purity, ]
(300 MHz, CDCl3) d 0.85-0.95 (m, 6H), 1.3ꢀ
12H), 2.1ꢀ2.25 (m, 2H), 2.48 (t, Jꢃ6.7 Hz, 2H), 5.63 (t,
Jꢃ7.2 Hz, 1H), 7.15ꢀ
7.35 (m, 5H). 13C-NMR (75
/
98%. H-NMR
/1.5 (m,
244.9824, Found 244.9826.
/
/
/
/
4.3.9. (1Z)-1-Chloro-1,2-diphenylethene
MHz, CDCl3) d 13.96, 14.10, 22.69, 22.71, 28.59, 29.14,
29.48, 29.92, 30.96, 31.85, 126.31 (3C), 128.08 (2C),
119.12, 140.06, 143.54.
1
Yield, 82%. Stereoisomeric purity, ]
(300 MHz, CDCl3) d 7.08 (s, 1H), 7.25ꢀ
7.7ꢀ
7.8 (m, 4H). 13C-NMR (75 MHz, CDCl3) d 126.06,
/
98%. H-NMR
/
7.45 (m, 6H),
/
126.68 (2C), 127.96, 128.24 (2C), 128.36 (2C), 128.70
(2C), 129.43, 132.04, 135.23, 139.22.
4.4.4. (2E)-2-(2?-Thienyl)-2-nonene
1
Yield, 92%. Stereoisomeric purity, ]
(300 MHz, CDCl3) d 0.89 (t, Jꢃ
(m, 8H), 2.03 (s, 3H), 2.17ꢀ2.25 (m, 2H), 5.94 (t, Jꢃ
Hz, 1H), 6.9ꢀ6.95 (m 2H), 7.0ꢀ
/
98%. H-NMR
/
6.4 Hz, 3H), 1.25ꢀ
/1.5
4.3.10. (1Z)-1-Chloro-4-trimethylsilyl-1-buten-3-yne
1
98%. H-NMR
/
/7.3
/
/
7.1 (m, 1H). 13C-NMR
Yield, 90%. Stereoisomeric purity, ]
/
(300 MHz, CDCl3) d 0.28 (s, 9H), 6.25 (s, 1H), 7.35ꢀ
(m, 3H), 7.55ꢀ
7.65 (m, 2H). 13C-NMR (75 MHz,
CDCl3) d ꢄ0.15, 100.88, 104.04, 107.01, 126.26 (2C),
128.47 (2C), 129.65, 136.45, 143.49. IR (neat) 3062,
3031, 2960, 2129, 1595, 1490, 1446, 1250, 1087 cmꢄ1
MS (CI) m/z (%) 235 (100) [Mꢁꢁ
1]. HRMS Calc. for
/7.4
(75 MHz, CDCl3) d 14.09, 15.70, 22.64, 28.48, 29.06,
29.49, 31.77, 121.77, 122.64, 127.12, 127.71, 128.61,
148.18. IR (neat) 3072, 2956, 2855, 1591, 1457, 1120
cmꢄ1. MS (CI) m/z (%) 209 (100) [Mꢁꢁ
1]. HRMS
/
/
/
.
Calc. for C13H20S 208.1286, Found 208.1294.
/
C13H15BrSi 234.0632, Found 234.0626.
4.4.5. (2E)-2-(2?-Thiazolyl)-2-nonene
1
Yield, 93%. Stereoisomeric purity, ]
(300 MHz, CDCl3) d 0.89 (t, Jꢃ7.4 Hz, 3H), 1.3ꢀ
(m, 8H), 2.15 (s, 3H), 2.2ꢀ2.3 (m, 2H), 6.46 (t, Jꢃ
/
98%. H-NMR
4.4. General procedure for the alkylation of (Z)-a-
/
/1.5
bromo- or chlorostyrenes
/
/7.3
Hz, 1H), 7.13 (d, Jꢃ
/
3.3 Hz, 1H), 7.71 (d, Jꢃ3.3 Hz,
/
A mixture of Pd(tBu3P)2 (5.1 mg, 0.01 mmol), a
monobromide or a monochloride (0.5 mmol), and an
alkylzinc reagent or methylmagnesium bromide (1.0
mmol) in THF (5 ml) was stirred at the temperature
indicated in Table 3. The reaction mixture was quenched
with aqueous NH4Cl at 0 8C, extracted with ether,
washed with brine, dried over Na2SO4, and evaporated
under vacuum. The crude product was subjected to
column chromatography (silica gel, hexanes) to give the
corresponding products.
1H). 13C-NMR (75 MHz, CDCl3) d 14.00, 14.80, 22.54,
28.54, 28.99 (2C), 31.65, 117.11, 129.75, 133.45, 142.61,
171.91.
4.4.6. (2E,4S)-4-Methyl-2-phenyl-2-hexene
Yield, 92%. Stereoisomeric purity, ]
/
98%. [a]2D3
ꢁ
/
1
50.1 (c 2.4, CHCl3). H-NMR (300 MHz, CDCl3) d
0.98 (t, Jꢃ7.3 Hz, 3H), 1.10 (d, Jꢃ6.7 Hz, 3H), 1.2ꢀ
1.6 (m, 2H), 2.11 (d, Jꢃ1.0 Hz, 3H), 2.4ꢀ2.65 (m, 1H),
5.63 (dd, Jꢃ8.4, 1.0 Hz, 1H), 7.25ꢀ
7.5 (m, 5H). 13C-
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