M. Xie et al. / Journal of Organometallic Chemistry 694 (2009) 2258–2262
2261
101.9, 50.9, 33.5, 31.9, 29.1, 22.3, 21.7, 14.0; HRMS (ESI), calcd for
C21H25INaO2S (MNa+), 491.0518, found, 491.0514; IR (KBr) 2954,
HRMS (ESI), calcd for C21H17BrNaO2S (MNa+), 435.0026, found,
435.0024; IR (KBr) 3061, 1595, 1489, 1328, 1155, 1087, 813 cmÀ1
.
1596, 1494, 1317, 1148, 1083 cmÀ1
.
3.1.15. (Z)-1-Bromo-2-phenyl-1-(p-tolylsulfonyl)-1-heptylene (4o)
3.1.8. (E)-1-Bromo-2,3-diphenyl-1-(p-tolylsulfonyl)-1-propylene (4h)
White solid; m.p. 96–97 °C; 1H NMR (300 MHz, C6D6) d 7.75 (d,
J = 8.2 Hz, 2H), 7.02–6.99 (m, 6H), 6.97–6.96 (m, 2H), 6.90–6.87 (m,
2H), 6.73 (d, J = 7.9 Hz, 2H), 3.81 (s, 2H), 1.89 (s, 3H); 13C NMR
(75 MHz, C6D6) d 153.6, 144.0, 138.0, 137.5, 135.5, 129.2, 129.1,
128.9, 128.5, 128.0, 127.9, 127.5, 127.0, 124.7, 48.5, 21.0; HRMS
(ESI), calcd for C22H19BrNaO2S (MNa+), 449.0187, found,
Colorless oil; 1H NMR (300 MHz, CDCl3) d 7.94–7.91 (m, 2H),
7.39–7.29 (m, 5H), 7.11–7.08 (m, 2H), 3.12 (t, J = 7.9 Hz, 2H), 2.45
(s, 3H), 1.39–1.25 (m, 6H), 0.84 (t, J = 6.6 Hz, 3H); 13C NMR
(75 MHz, CDCl3) d 154.1, 144.8, 139.9, 136.6, 129.7, 129.2, 128.3,
128.1, 126.6, 120.3, 36.2, 31.5, 27.7, 22.2, 21.6, 13.8; HRMS (ESI),
calcd for C20H23BrNaO2S (MNa+), 429.0501, found, 429.0498; IR
(KBr) 3047, 2953, 1592, 1489, 1315, 1149, 1083 cmÀ1
.
449.0187; IR (KBr) 3058, 1594, 1491, 1332, 1152, 1085 cmÀ1
.
3.1.16. 1-Chloro-2, 2-diphenyl-1-(p-tolylsulfonyl)ethylene (4p)
White solid; m.p. 169–170 °C; 1H NMR (300 MHz, CDCl3) d 7.71
(d, J = 8.1 Hz, 2H), 7.35–7.25 (m, 8H), 7.21–7.19 (m, 4H), 2.45 (s,
3H); 13C NMR (75 MHz, CDCl3) d 151.0, 144.8, 139.7, 138.0,
136.2, 130.5, 129.5, 129.1, 128.9, 128.8, 128.6, 128.3, 128.1,
127.9, 21.7; HRMS (ESI), calcd for C21H17ClNaO2S (MNa+),
391.0535, found, 391.0530; IR (KBr) 3049, 1648, 1595, 1492,
3.1.9. (Z)-2-Benzyl-1-bromo-1-(p-tolylsulfonyl)-1-heptylene (4i)
White solid; m.p. 94–95 °C; 1H NMR (300 MHz, CDCl3) d 7.85 (d,
J = 8.2 Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 7.28–7.22 (m, 3H), 7.10 (d,
J = 7.4 Hz, 2H), 3.78 (s, 2H), 2.74 (t, J = 7.8 Hz, 2H), 2.45 (s, 3H),
1.55–1.45 (m, 2H), 1.35–1.22 (m, 4H), 0.87 (t, J = 6.7 Hz, 3H); 13C
NMR (75 MHz, CDCl3) d 156.8, 144.8, 136.9, 136.4, 129.7, 128.5,
128.3, 127.9, 127.0, 120.6, 45.2, 33.3, 31.9, 29.1, 22.3, 21.7, 14.0;
HRMS (ESI), calcd for C21H25BrNaO2S (MNa+), 443.0656, found,
1329, 1158, 1088, 816 cmÀ1
.
443.0650; IR (KBr) 3058, 2957, 1595, 1491, 1333, 1152, 1086 cmÀ1
.
3.2. Procedure for the preparation of 5 by Negishi coupling reaction of
vinyl iodide 4a and vinylzinc bromide 3a
3.1.10. (E)-1-Iodo-2-phenyl-1-(p-tolylsulfonyl)-1-hexylene (4j)
White solid; m.p. 77–79 °C; 1H NMR (300 MHz, CDCl3) d 7.40 (d,
J = 8.3 Hz, 2H), 7.28–7.23 (m, 3H), 7.13–7.10 (m, 2H), 6.94–6.91 (m,
2H), 2.63 (t, J = 7.4 Hz, 2H), 2.38 (s, 3H), 1.35–1.25 (m, 4H), 0.85 (t,
J = 6.7 Hz, 3H); 13C NMR (75 MHz, CDCl3) d 162.4, 143.9, 138.1,
136.3, 129.1, 128.5, 127.9, 127.7, 127.6, 103.6, 48.5, 28.4, 22.4,
21.6, 13.8; HRMS (ESI), calcd for C19H21INaO2S (MNa+), 463.0205,
found, 463.0201; IR (KBr) 2951, 2924, 1594, 1491, 1314, 1147,
Vinyl iodide 4a (0.5 mmol), Ni(PPh3)2Cl2 (10 mol%) and 3.0 mL
of THF were added successively to the THF solution of vinylzinc
bromide 3a, which was prepared in situ from 1-phenyl-2-(p-toly-
lsulfonyl)ethyne 1a (0.6 mmol) and allylzinc bromide (0.6 mmol).
The reaction mixture was stirred at 50 °C overnight. The reaction
was quenched with saturated NH4Cl solution. After usual workup,
the crude product was purified by flash chromatography on silica
gel (hexane/ethyl acetate = 15:1 v/v) to give the desired pure prod-
uct 5.
1083 cmÀ1
.
3.1.11. (E)-1-Chloro-2-phenyl-1-(p-tolylsulfonyl)-1-hexylene (4k)
White solid; m.p. 55–57 °C; 1H NMR (300 MHz, CDCl3) d 7.55 (d,
J = 8.3 Hz, 2H), 7.33–7.31 (m, 3H), 7.23–7.20 (m, 2H), 7.09–7.06 (m,
2H), 2.56 (t, J = 7.6 Hz, 2H), 2.38 (s, 3H), 1.34–1.25 (m, 4H), 0.82 (t,
J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3) d 152.7, 144.6, 137.7,
136.4, 129.5, 128.9, 128.2, 127.9, 127.6, 127.1, 39.6, 28.9, 22.5,
21.7, 13.8; HRMS (ESI), calcd for C19H21ClNaO2S (MNa+),
371.0848, found, 371.0843; IR (KBr) 3058, 2952, 1595, 1490,
3.2.1. (4Z,6Z)-4,7-Diphenyl-5,6-bis(p-tolylsulfonyl)-1,4,6,9-
decatetraene (5)
White solid; m.p. 124–126 °C; 1H NMR (300 MHz, CDCl3) d 7.49
(d, J = 8.1 Hz, 4H), 7.21–7.11 (m, 4H), 7.06–6.92 (m, 10H), 5.60–
5.47 (m, 2H), 5.03–4.96 (m, 4H), 3.91–3.83 (m, 2H), 3.43–3.37
(m, 2H), 2.32 (s, 6H); 13C NMR (75 MHz, CDCl3) d 157.4, 143.0,
142.9, 138.3, 136.6, 132.2, 128.7, 128.4, 127.8, 127.6, 127.4,
118.8, 44.4, 21.5; MS (ESI), 617.1 (MNa+); Anal. Calcd. for
C36H34O4S2, C, 72.70; H, 5.76. Found: C, 72.65; H, 5.74%. IR (KBr)
1442, 1322, 1157, 1083, 811 cmÀ1
.
3.1.12. 1, 1-Diphenyl-2-iodo-2-(p-tolylsulfonyl)ethylene (4l)
3048, 2834, 1568, 1441, 1308, 1152 cmÀ1
.
White solid; m.p. 183–185 °C; 1H NMR (300 MHz, CDCl3) d 7.55
(d, J = 8.3 Hz, 2H), 7.30–7.09 (m, 12H), 2.40 (s, 3H); 13C NMR
(75 MHz, CDCl3) d 161.7, 145.7, 144.2, 138.6, 136.1, 129.2, 128.7,
128.6, 128.5, 127.8, 127.6, 103.9, 21.6; HRMS (ESI), calcd for
C21H17INaO2S (MNa+), 482.9892, found, 482.9899; IR (KBr) 3062,
Acknowledgments
The authors are grateful to the National Natural Science Foun-
dation of China (Nos. 20672001 and 20772001) and the Anhui Edu-
cation Department (No. TD200707) for financial support of this
work. We are also grateful to Prof. Jiping Hu, Hongtao Zhang and
Yun Wei for their helpful assistances.
1593, 1490, 1310, 1302, 1145, 1082 cmÀ1
.
3.1.13. (Z)-1-Iodo-2-phenyl-1-(p-tolylsulfonyl)-1-heptylene (4m)
White solid; m.p. 81–82 °C; 1H NMR (300 MHz, CDCl3) d 7.94–
7.92 (m, 2H), 7.38–7.32 (m, 5H), 7.04–7.01 (m, 2H), 3.09 (t,
J = 8.1 Hz, 2H), 2.46 (s, 3H), 1.35–1.21 (m, 6H), 0.82 (t, J = 6.8 Hz,
3H); 13C NMR (75 MHz, CDCl3) d 165.2, 146.1, 144.6, 136.8,
129.6, 128.4, 128.3, 128.1, 126.4, 100.9, 36.5, 31.5, 27.6, 22.2,
21.6, 13.8; HRMS (ESI), calcd for C20H23INaO2S (MNa+), 477.0361,
found, 477.0355; IR (KBr) 3047, 2952, 1634, 1592, 1489, 1346,
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
1145, 1049 cmÀ1
.
References
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(2008) 3787.
3.1.14. 1-Bromo-2,2-diphenyl-1-(p-tolylsulfonyl)ethylene (4n)
White solid; m.p. 170–171 °C; 1H NMR (300 MHz, CDCl3) d 7.68
(d, J = 8.2 Hz, 2H), 7.32–7.25 (m, 8H), 7.19–7.17 (m, 4H), 2.43 (s,
3H); 13C NMR (75 MHz, CDCl3) d 154.9, 144.6, 141.9, 138.6,
136.3, 129.4, 129.0, 128.8, 128.7, 128.3, 128.1, 127.9, 122.8, 21.6;
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