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G. Hilt et al.
PAPER
6.8 Hz, 1 H, Holef), 5.13 (dt, J = 17.2, 1.5 Hz, 1 H, Holef), 4.98 (dt,
J = 10.2, 1.3 Hz, 1 H, Holef), 3.55–3.50 (m, 1 H, CH), 3.00 (ddd,
J = 16.6, 6.1, 2.6 Hz, 1 H, CHH), 2.82 (dd, J = 16.6, 2.3 Hz, 1 H,
CHH).
13C NMR (75 MHz, CDCl3): d = 140.7, 139.8, 138.8, 137.3, 134.4,
128.4, 127.1, 125.4, 125.1, 121.8, 121.1, 114.9, 39.6, 32.5.
Abel, E. W.; Stone, F. G. A.; Wilkinson, G., Eds.; Pergamon
Press: Oxford, 1995, 741. (g) Schore, N. E. In
Comprehensive Organic Synthesis, Vol. 5; Trost, B. M.;
Fleming, I., Eds.; Pergamon Press: Oxford, 1991, 1129.
(h) Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984,
23, 539; Angew. Chem. 1984, 96, 525.
(2) (a) Hilt, G.; Smolko, K. I. Angew. Chem. Int. Ed. 2003, 42,
2795; Angew. Chem. 2003, 115, 2901. (b) Hilt, G.; Hess,
W.; Harms, K. Org. Lett. 2006, 8, 3287.
MS (EI): m/z (%) = 258 (100, [M]+), 241 (26), 230 (30), 217 (21),
202 (13), 289 (8), 179 (21), 165 (33), 152 (23), 141 (12), 128 (13).
(3) (a) Hilt, G.; Lüers, S. Synthesis 2002, 609. (b) Grutters, M.
M. P.; Müller, C.; Vogt, D. J. Am. Chem. Soc. 2006, 128,
7414. (c) Bianchini, C.; Giambastiani, G.; Meli, A.; Toti, A.
Organometallics 2007, 26, 1303.
HRMS (EI): m/z calcd for C20H18: 258.1409; found: 258.1399.
1,4-Diphenyl-5-vinylbenzene (6)
Eluent: pentane; colorless oil; yield: 37%; ~85% pure.
(4) (a) Hilt, G.; Vogler, T.; Hess, W.; Galbiati, F. Chem.
Commun. 2005, 1474. (b) Doszczak, L.; Fey, P.; Tacke, R.
Synlett 2007, 753. (c) Chang, H. T.; Jeganmohan, M.;
Cheng, C. H. Org. Lett. 2007, 9, 505. (d) Saino, N.;
Amemiya, F.; Tanabe, E.; Kase, K.; Okamoto, S. Org. Lett.
2006, 8, 1439. (e) Wu, M. S.; Shanmugasundaram, M.;
Cheng, C. H. Chem. Commun. 2003, 718. (f) Yong, L.;
Butenschön, H. Chem. Commun. 2002, 2852. (g) Sugihara,
T.; Wakabayashi, A.; Nagai, Y.; Takao, H.; Imagawa, H.;
Nishizawa, M. Chem. Commun. 2002, 576. (h) Sigman, M.
S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120,
5130.
1H NMR (300 MHz, CDCl3): d = 7.86 (d, J = 1.9 Hz, 1 H, Har),
7.68–7.65 (m, 2 H, Har), 7.56 (dd, J = 7.9, 1.9 Hz, 2 H, Har), 7.50–
7.30 (m, 8 H, Har), 6.77 (dd, J = 17.6, 10.9 Hz, 1 H, Holef), 6.50 (dd,
J = 17.4, 1.3 Hz, 1 H, Holef), 5.92 (dd, J = 10.9, 1.1 Hz, 1 H, Holef).
MS (EI): m/z (%) = 256 (100, [M]+), 239 (38), 226 (7), 178 (19),
165 (12), 151 (7).15
2-Methyl-1,4-diphenyl-3-vinylbenzene (7)
Eluent: pentane–MTBE (10:1); colorless oil; yield: 31%; 95% pure.
1H NMR (300 MHz, CDCl3): d = 7.48–7.30 (m, 10 H, Har), 7.22 (s,
2 H, Har), 6.68 (dd, J = 17.9, 11.5 Hz, 1 H, Holef), 5.37 (dd, J = 11.5,
1.9 Hz, 1 H, Holef), 5.11 (dd, J = 17.9, 1.9 Hz, 1 H, Holef), 2.30 (s, 3
H, CH3).
13C NMR (75 MHz, CDCl3): d = 142.4, 142.3, 141.9, 140.4, 137.3,
135.7, 133.6, 130.0, 129.4, 128.5, 128.1, 127.8, 127.5, 126.8, 126.5,
120.7, 18.8.
MS (EI): m/z = 270 (84, [M]+), 255 (100, [M – CH3]+), 239 (38),
226 (8), 215 (6), 202 (5), 189 (10), 178 (16), 165 (9), 152 (6), 139
(3), 126 (20), 113 (9), 101 (5), 91 (4), 77 (6).
(5) Hilt, G.; Hess, W.; Vogler, T.; Hengst, C. J. Organomet.
Chem. 2005, 690, 5170.
(6) (a) Hilt, G.; Treutwein, J. Angew. Chem. Int. Ed. 2007, 46,
8500; Angew. Chem. 2007, 119, 8653. (b) Petit, M.; Aubert,
C.; Malacria, M. Org. Lett. 2004, 6, 3937.
(7) Hilt, G.; Janikowski, J.; Hess, W. Angew. Chem. Int. Ed.
2006, 45, 5204; Angew. Chem. 2006, 118, 5328.
(8) This type of product was also observed in a rhodium-
catalyzed cyclization process, see: (a) Brenner, W.;
Heimbach, P.; Ploner, K. J.; Thoemel, F. Angew. Chem., Int.
Ed. Engl. 1969, 8, 753; Angew. Chem. 1969, 81, 744.
(b) Wender, P. A.; Deschamps, N. M.; Williams, T. J.
Angew. Chem. Int. Ed. 2004, 43, 3076; Angew. Chem. 2004,
116, 3138.
HRMS (EI): calcd for C20H18: 258.1409; found: 258.1414.
Acknowledgment
We are grateful to Mr. Vesal Naseri for preparing a suitable crystal
of the [CoBr(dppben)2]·[CoBr3(thf)]·CH2Cl2 complex.
(9) The ratios were determined by GC/GCMS analysis. The
missing percentages result from unidentified side products.
(10) CCDC 659433 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
(11) The quality of the crystal was significantly reduced by
disordered solvent within the crystal cell.
(12) Carlin, R. L.; Chirico, R. D.; Sinn, E.; Mennenga, G.; de
Jongh, L. J. Inorg. Chem. 1982, 21, 2218.
References
(1) For reviews on cobalt-catalyzed cycloaddition processes
see: (a) Omae, I. Appl. Organomet. Chem. 2007, 21, 318.
(b) Malacria, M.; Aubert, C.; Renaud, J. L. In Science of
Synthesis, Vol. 1; Lautens, M., Ed.; Thieme: Stuttgart, 2001,
439. (c) Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100,
2901. (d) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R.
J. Chem. Rev. 1996, 96, 635. (e) Lautens, M.; Klute, W.;
Tam, W. Chem. Rev. 1996, 96, 49. (f) Grotjahn, D. B.
In Comprehensive Organometallic Chemistry II, Vol. 12;
(13) Gandon, V.; Agenet, N.; Vollhardt, K. P. C.; Malacria, M.;
Aubert, C. J. Am. Chem. Soc. 2006, 128, 8509.
(14) The Rf values of TLC analysis utilizing pentane as the eluent
span a range between 0.75 and 0.90.
(15) 1H NMR data were assigned of the major component to the
best of our knowledge and 13C NMR and HRMS data were
not obtained based on the low purity of the sample.
Synthesis 2008, No. 1, 75–78 © Thieme Stuttgart · New York