2686
B. Huang et al. / Journal of Organometallic Chemistry 696 (2011) 2685e2688
2. Experimental
2.2.6. (E)-1-(4-Chlorophenyl)-1-octene, 3f [52]
Colorless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.62-7.59 (m, 2H),
2.1. General remarks
7.10-7.08 (m, 2H), 6.33 (d, J ¼ 16.0 Hz, 1H), 6.22 (dt, J ¼ 16.0, 6.8 Hz,
1H), 2.24-2.17 (m, 2H), 1.49-1.42 (m, 2H), 1.38-1.25 (m, 6H), 0.91 (t,
All chemicals were of reagent grade and used as purchased. All
products were characterized by comparison of their spectra and
physical data with authentic samples. IR spectra were determined
on a PerkineElmer 683 instrument. 1H NMR spectra were recorded
on a Bruker AC-P400 (400 MHz) spectrometer with TMS as an
internal standard in CDCl3 as solvent. 13C NMR spectra were
recorded on a Bruker AC-P400 (100 MHz) spectrometer in CDCl3 as
solvent. Microanalyses were measured using a Yanaco MT-3 CHN
microelemental analyzer. Melting points are uncorrected.
J ¼ 7.0 Hz, 3H) ppm. IR (film):
n
¼ 2957, 2927, 1707, 1594, 1490, 1091,
964, 809 cmꢁ1
.
2.2.7. (E)-1-Phenyl-3-methoxypropene, 3g [53]
Colorless oil. 1H NMR (400 MHz, CDCl3):
6.61 (d, J ¼ 16.0 Hz, 1H), 6.28 (dt, J ¼ 16.0, 6.0 Hz, 1H), 4.09 (d,
J ¼ 6.0 Hz, 2H), 3.39 (s, 3H) ppm. IR (film): ¼ 2926, 2821, 1658,
1599, 1449, 1191, 1121, 1029, 967, 743 cmꢁ1
d
¼ 7.40-7.22 (m, 5H),
n
.
2.2.8. (E)-1-(4-Chlorophenyl)-3-methoxypropene, 3h[54]
Colorless oil. 1H NMR (400 MHz, CDCl3):
¼ 7.33-7.25 (m, 4H),
6.56 (d, J ¼ 16.0 Hz, 1H), 6.25 (dt, J ¼ 16.0, 6.0 Hz, 1H), 4.08 (d,
J ¼ 6.0 Hz, 2H), 3.39 (s, 3H) ppm. IR (film): ¼ 2925, 2823, 1683,
1593, 1491, 1191, 1090, 1012, 968, 846, 796 cmꢁ1
2.2. General procedure for the hydrozirconation/cross-coupling
tandem reaction of terminal alkynes with aryl halides in [bmim]
[PF6]
d
n
.
In a 20 mL two-necked round-bottom flask, equipped with
a magnetic stirrer bar, was placed 2 mL of [bmim][PF6]. The flask
was then degassed under reduced pressure at room temperature
for 1 h, and argon gas was then introduced. To the ionic liquid were
added terminal alkyne (1 mmol) and Cp2Zr(H)Cl (1.1 mmol), and
the resulting mixture was stirred at 30 ꢀC for 1 h. Then aryl halide
(1 mmol) and Pd(PPh3)4 (0.05 mmol) were added and the mixture
was stirred at 60e80 ꢀC for 12 h. Product was extracted from the
reaction mixture by the addition of light petroleum ether (8 mL),
followed by decanting off a petroleum ether solution of the prod-
ucts. This was repeated two additional times. After evaporation, the
residue was purified by flash chromatography on silica gel using
light petroleum ether as the eluent.
2.2.9. (E)-1-(4-Methylphenyl)-2-phenylethene, 3i
White solid. 118e119 ꢀC (lit [55]. m.p. 120 ꢀC). 1H NMR
(400 MHz, CDCl3):
7.35 (t, J ¼ 7.6 Hz, 2H), 7.28-7.22 (m, 1H), 7.16 (d, J ¼ 8.4 Hz, 2H), 7.07
(d, J ¼ 2.4 Hz, 2H), 2.36 (s, 3H) ppm. IR (KBr): ¼ 3024, 2918, 1643,
1595, 1511, 1448, 970, 809, 690 cmꢁ1
d
¼ 7.50 (d, J ¼ 7.2 Hz, 2H), 7.41 (d, J ¼ 8.0 Hz, 2H),
n
.
2.2.10. (E)-1,2-Diphenylethene, 3j
White solid. 124 ꢀC (lit [56]. m.p. 124 ꢀC). 1H NMR (400 MHz,
CDCl3):
¼ 7.53-7.51 (m, 4H), 7.38-7.33 (m, 4H), 7.28-7.23 (m, 2H),
7.11 (s, 2H) ppm. IR (KBr):
¼ 3019, 1597, 1576, 1495, 1451, 962, 765,
692 cmꢁ1
d
n
.
2.2.1. (E)-1-(4-Methoxyphenyl)-1-hexene, 3a[49]
2.2.11. (E)-1-(4-Chlorophenyl)-2-phenylethene, 3k
Colorless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.27 (d, J ¼ 8.4 Hz,
White solid. 127e128 ꢀC (lit [57]. m.p. 129 ꢀC). 1H NMR
2H), 6.83 (d, J ¼ 8.4 Hz, 2H), 6.32 (d, J ¼ 16.0 Hz, 1H), 6.09 (dt,
(400 MHz, CDCl3):
7.38-7.27 (m, 5H), 7.07 (d, J ¼ 2.8 Hz, 2H) ppm. IR (KBr):
1643, 1588, 1494, 1448, 1090, 966, 817, 691 cmꢁ1
d
¼ 7.50 (d, J ¼ 7.2 Hz, 2H), 7.44 (d, J ¼ 8.8 Hz, 2H),
J ¼ 16.0, 7.2 Hz, 1H), 3.80 (s, 3H), 2.22-2.16 (m, 2H), 1.46-1.34 (m,
n
¼ 3019,
4H), 0.93 (t, J ¼ 7.4 Hz, 3H) ppm. IR (film):
n
¼ 2957, 2929,1608,1511,
.
1248, 1174, 1038, 965, 804 cmꢁ1
.
2.2.12. (E)-1-(4-Methoxyphenyl)-2-phenylethene, 3l
White solid. 134e135 ꢀC (lit [58]. m.p. 136 ꢀC). 1H NMR
(400 MHz, CDCl3):
2.2.2. (E)-1-(4-Chlorophenyl)-1-hexene, 3b [49]
Colorless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.59 (d, J ¼ 8.4 Hz,
d
¼ 7.49 (d, J ¼ 7.6 Hz, 2H), 7.45 (d, J ¼ 8.4 Hz, 2H),
2H), 7.07 (d, J ¼ 8.4 Hz, 2H), 6.31 (d, J ¼ 16.0 Hz, 1H), 6.20 (dt,
J ¼ 16.0, 7.2 Hz, 1H), 2.21-2.17 (m, 2H), 1.45-1.34 (m, 4H), 0.92 (t,
7.34 (t, J ¼ 7.6 Hz, 2H), 7.23 (t, J ¼ 7.6 Hz,1H), 7.07 (d, J ¼ 16.4 Hz,1H),
6.97 (d, J ¼ 16.4 Hz, 1H), 6.90 (d, J ¼ 8.8 Hz, 2H), 3.83 (s, 3H) ppm. IR
J ¼ 7.2 Hz, 3H) ppm. IR (film):
n
¼ 2957, 2927, 1650, 1593, 1470, 1091,
(KBr):
n
¼ 3050, 1603, 1500, 1252, 1170, 968, 820, 750 cmꢁ1
.
1005, 966, 809 cmꢁ1
.
2.2.13. (E)-1-(4-Chlorophenyl)-4-methoxy-1-butene, 3m
Colorless oil. 1H NMR (400 MHz, CDCl3):
2.2.3. (E)-1-(4-Methoxyphenyl)-1-octene, 3c [50]
Colorless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.11-7.06 (m, 2H),
d
¼ 7.28-7.25 (m, 2H),
6.23 (d, J ¼ 16.0 Hz, 1H), 6.04 (dt, J ¼ 16.0, 7.2 Hz, 1H), 3.33 (t,
6.85-6.82 (m, 2H), 6.32 (d, J ¼ 16.0 Hz, 1H), 6.08 (dt, J ¼ 16.0, 7.0 Hz,
J ¼ 6.8 Hz, 2H), 3.19 (s, 3H), 2.33-2.28 (m, 2H) ppm. 13C NMR
1H), 3.80 (s, 3H), 2.21-2.15 (m, 2H), 1.47-1.42 (m, 2H), 1.36-1.23 (m,
(100 MHz, CDCl3):
d
¼ 135.97, 132.54, 130.38, 128.57, 127.80, 127.24,
6H), 0.89 (t, J ¼ 6.8 Hz, 3H) ppm. IR (film):
n
¼ 2957, 2925, 1608,
72.07, 58.72, 33.40 ppm. IR (film):
n
¼ 3028, 2926, 1652, 1594, 1491,
1511, 1250, 1174, 1039, 964, 805 cmꢁ1
.
1119, 1093, 967, 806 cmꢁ1. Anal. Calcd. for C11H13OCl: C, 67.16; H,
6.66. Found: C, 66.89; H, 6.81.
2.2.4. (E)-1-Phenyl-1-octene, 3d [50]
Colorless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.36-7.16 (m, 5H),
2.2.14. (E)-1-(4-Methoxyphenyl)-2-cyclopropylethene, 3n[59]
6.37 (d, J ¼ 16.0 Hz, 1H), 6.22 (dt, J ¼ 16.0, 6.8 Hz, 1H), 2.23-2.17 (m,
White solid. 47e48 ꢀC 1H NMR (400 MHz, CDCl3):
d
¼ 7.23 (d,
2H), 1.48-1.42 (m, 2H), 1.38-1.25 (m, 6H), 0.89 (t, J ¼ 6.8 Hz, 3H)
J ¼ 8.8 Hz, 2H), 6.82 (d, J ¼ 8.8 Hz, 2H), 6.42 (d, J ¼ 15.6 Hz, 1H), 5.59
(dd, J ¼ 15.6, 8.8 Hz, 1H), 3.79 (s, 3H), 1.57-1.51 (m, 1H), 0.82-0.77
ppm. IR (film):
n
¼ 2956, 2926, 1707, 1598, 1449, 962, 742, 692 cmꢁ1
.
(m, 2H), 0.50-0.46 (m, 2H) ppm. IR (KBr):
n
¼ 2955, 1642, 1607, 1567,
2.2.5. (E)-1-(4-Methylphenyl)-1-octene, 3e [51]
Colorless oil. 1H NMR (400 MHz, CDCl3):
1512, 1163, 1074, 955, 861 cmꢁ1
.
d
¼ 7.23 (d, J ¼ 7.6 Hz,
2H), 7.09 (d, J ¼ 7.6 Hz, 2H), 6.34 (d, J ¼ 16.0 Hz, 1H), 6.15 (dt,
J ¼ 16.0, 7.2 Hz, 1H), 2.31 (s, 3H), 2.21-2.15 (m, 2H), 1.47-1.41 (m,
2H), 1.38-1.24 (m, 6H), 0.89 (t, J ¼ 7.2 Hz, 3H) ppm. IR (film):
2.2.15. (E)-1-(2-thienyl)-2-cyclopropylethene, 3o
Colorless oil. 1H NMR (400 MHz, CDCl3):
d
¼ 7.04 (d, J ¼ 5.2 Hz,
1H), 6.93-6.90 (m, 1H), 6.82 (d, J ¼ 3.6 Hz, 1H), 6.59 (d, J ¼ 15.6 Hz,
n
¼ 2957, 2925, 1603, 1597, 1448, 963, 807 cmꢁ1
.
1H), 5.59 (dd, J ¼ 15.6, 9.2 Hz, 1H), 1.57-1.48 (m, 1H), 0.83-0.78 (m,