| Автор | Osakada, Kohtaro |
| Автор | Takimoto, Hisami |
| Автор | Yamamoto, Takakazu |
| Дата выпуска | 1999 |
| dc.description | 1-Aryl-2-methylenecyclopropanes reacted with [RhCl(PPh3)3] at 50â °C to give [RhCl(η<sup>4</sup>-CH2.dbd6;CArCH.dbd6;CH2)(PPh3)2] (Arâ =â C6H5 1a, C6H4F-p 1b, C6H4Me-p 1c or C6H4OMe-p 1d) via ring opening isomerization of the substrate and its subsequent co-ordination to Rh. The diene-co-ordinated rhodium complexes have been characterized by X-ray crystallography and NMR spectroscopy. Similar reaction at 0â °C afforded the rhodium(I) complexes with Ï -co-ordinated 1-aryl-2-methylenecyclopropane, [RhCl(η<sup>2</sup>-CH2.dbd6;.ub1s;CCH2C.ub1e;HAr)(PPh3)2] (Arâ =â C6H5 2a, C6H4F-p 2b, C6H4Me-p 2c or C6H4OMe-p 2d). Exchange of the ligand of 2a with added 1-aryl-2-methylenecyclopropanes occurs reversibly at 30â 45â °C with the thermodynamic parameters of the reactions 2aâ +â CH2.dbd6;.ub1s;CCH2C.ub1e;HC6H4X-pâ â â 2b (or 2c)â +â CH2.dbd6;.ub1s;CCH2C.ub1e;HC6H5 being Î Hâ °â =â â 10.3 kJ mol<sup>â 1</sup> and Î Sâ °â =â â 32 J K<sup>â 1</sup> mol<sup>â 1</sup> for Xâ =â F and Î Hâ °â =â 2.2 kJ mol<sup>â 1</sup> and Î Sâ °â =â â 2.6 J K<sup>â 1</sup> mol<sup>â 1</sup> for Xâ =â Me, respectively, at 298 K. The structure of a PEt3 co-ordinated analog, [RhCl(η<sup>2</sup>-CH2.dbd6;.ub1s;CCH2C.ub1e;HC6H4Me-p)(PEt3)2] 3c, has been determined by X-ray crystallography. The reaction of 1-methylene-2-phenylcyclopropane with [RhCl(PPh3)3] at 25â °C gave a mixture of 1a and 2a. Heating of a benzene solution of 2a at 50â °C turned it into 1a in low yield (<7%), while the reactions of 1-methylene-2-phenylcyclopropane with 2a at the same temperature gave 1a (10%) and 2-phenylbuta-1,3-diene (14%). The amounts of the products formed via ring opening isomerization in these reactions are much smaller than those in the reaction of 1-methylene-2-phenylcyclopropane with [RhCl(PPh3)3] at 50â °C. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Reaction of 1-aryl-2-methylenecyclopropanes with rhodium(I) complexes leading to ring opening isomerization and π co-ordination of the CC double bond |
| Тип | research-article |
| DOI | 10.1039/a808906j |
| Electronic ISSN | 1364-5447 |
| Print ISSN | 1472-7773 |
| Журнал | Journal of the Chemical Society, Dalton Transactions |
| Первая страница | 853 |
| Последняя страница | 860 |
| Выпуск | 6 |
| Библиографическая ссылка | K. B. Wiberg, S. M. Bachrach, Angew. Chem., Int. Ed. Engl., 1986, 25, 312, J. Phys. Chem., 1993, 97, 4496 |
| Библиографическая ссылка | W. A. Donaldson, R. Noyori, T. Odagi, H. Takaya, R. Noyori, Y. Kumagai, I. Umeda, H. Takaya, R. Noyori, T. Ishigami, N. Hayashi, H. Takaya, P. Binger, U. Schuchardt, S. Yamago, E. Nakamura, W. B. Motherwell, M. Shipman, M. Lautens, Y. Ren, P. H. M. Delanghe, M. Lautens, C. Meyer, A. Lorenz, N. Tsukada, A. Shibuya, I. Nakamura, Y. Yamamoto, R. J. Boffey, M. Santagostino, W. G. Whittingham, J. D. Kilburn, Adv. Met.-Org. Chem., 1991, 2, 269, J. Am. Chem. Soc., 1970, 92, 5780, J. Am. Chem. Soc., 1972, 94, 4018, J. Am. Chem. Soc., 1973, 95, 1674, Chem. Ber., 1980, 113, 3334, J. Chem. Soc., Chem. Commun., 1988, 1112, Tetrahedron Lett., 1991, 32, 1103, J. Am. Chem. Soc., 1994, 116, 8821, J. Am. Chem. Soc., 1996, 118, 10676, J. Am. Chem. Soc., 1997, 119, 8123, Chem. Commun., 1998, 1875 |
| Библиографическая ссылка | L. Jia, X. Yang, A. M. Seyam, I. D. L. Albert, P. Fu, S. Yang, T. J. Marks, J. Am. Chem. Soc., 1996, 118, 7900, and refs. therein |
| Библиографическая ссылка | G. Parkin, E. Bunel, B. J. Burger, M. S. Trimmer, A. van Asselt, J. E. Bercaw, J. Mol. Catal., 1987, 41, 21 |
| Библиографическая ссылка | W. E. Billups, L.-P. Lin, B. A. Baker, T. H. Whitesides, R. W. Slaven, T. H. Whitesides, R. W. Slaven, J. C. Calabrese, A. R. Pinhas, A. G. Samuelson, R. Risemberg, E. V. Arnoid, J. Clardy, B. K. Carpenter, S. R. Allen, S. G. Barnes, M. Green, G. Moran, L. Trollope, N. W. Murrall, A. J. Walch, D. M. Sharaiha, J. Organomet. Chem., 1973, 61, C55, J. Organomet. Chem., 1974, 67, 99, Inorg. Chem., 1974, 13, 1895, J. Am. Chem. Soc., 1981, 103, 1668, J. Chem. Soc., Dalton Trans., 1984, 1157 |
| Библиографическая ссылка | M. Green, R. P. Hughes, J. Chem. Soc., Chem. Commun., 1974, 686 |
| Библиографическая ссылка | K. Mashima, H. Takaya, K. Mashima, N. Sakai, H. Takaya, Organometallics, 1985, 4, 1464, Bull. Chem. Soc. Jpn., 1991, 64, 2475 |
| Библиографическая ссылка | D. M. Roundhill, D. N. Lawson, G. Wilkinson, H. C. Volger, H. Hogeveen, M. M. P. Gaasbeek, T. J. Katz, S. Cerefice, L. Cassar, J. Halpern, F. J. McQuillin, K. C. Powell, H. Ogoshi, J.-I. Setsune, Z.-I. Yoshida, N. W. Alcock, J. M. Brown, J. A. Conneely, D. H. Williamson, R. A. Periana, R. G. Bergman, J. Chem. Soc. A, 1968, 845, J. Am. Chem. Soc., 1969, 91, 218 and 2137, J. Am. Chem. Soc., 1969, 91, 2405, Chem. Commun., 1970, 1082, J. Chem. Soc., Dalton Trans., 1972, 2129, J. Chem. Soc., Chem. Commun., 1975, 572, J. Chem. Soc., Perkin Trans. 2, 1979, 962, J. Am. Chem. Soc., 1984, 106, 7272 |
| Библиографическая ссылка | J. M. Brown, A. G. Kent, G. P. Chiusoli, M. Costa, L. Meli, J. Chem. Soc., Perkin Trans. 2, 1987, 1597, J. Organomet. Chem., 1988, 358, 495 |
| Библиографическая ссылка | C.-H. Jun, Y.-G. Lim, Bull. Korean Chem. Soc., 1989, 10, 468 |
| Библиографическая ссылка | G. P. Chiusoli, M. Costa, P. Schianchi, G. Salerno, J. Organomet. Chem., 1986, 315, C45 |
| Библиографическая ссылка | M. Green, J. A. K. Howard, R. P. Hughes, S. C. Kellett, P. Woodward, J. Chem. Soc., Dalton Trans., 1975, 2007 |
| Библиографическая ссылка | J. Foerstner, A. Kakoschke, D. Stellfeldt, H. Butenschon, R. Wartchow, Organometallics, 1998, 17, 893 |
| Библиографическая ссылка | M. Murakami, K. Itami, M. Ubukata, I. Tsuji, Y. Ito, J. Org. Chem., 1998, 63, 4 |
| Библиографическая ссылка | P. Binger, T. R. Martin, R. Benn, A. Rufinska, G. Schroth, Z. Naturforsch., Teil B, 1984, 39, 993 |
| Библиографическая ссылка | K. Osakada, H. Takimoto, T. Yamamoto, Organometallics, 1998, 17, 4532 |
| Библиографическая ссылка | L. Porri, A. Lionetti, G. Allegra, A. Immirzi, L. Porri, A. Lionetti, S. M. Nelson, M. Sloan, M. G. B. Drew, R. R. Schrock, J. A. Osborn, B. F. G. Johnson, J. Lewis, D. J. Yarrow, E. W. Abel, T. Blackmore, R. J. Whitley, P. Caddy, M. Green, J. A. K. Howard, J. M. Squire, N. J. White, J. Moreto, K. Maruya, P. M. Bailey, P. M. Maitlis, P. Powell, M. Stephens, A. Muller, M. G. B. Drew, F. Claret, P. Vogel, M. Murakami, K. Itami, Y. Ito, Chem. Commun., 1965, 336, J. Organomet. Chem., 1966, 6, 422, J. Chem. Soc., Dalton Trans., 1973, 2195, J. Am. Chem. Soc., 1971, 93, 2397, J. Chem. Soc., Dalton Trans., 1972, 2084, J. Chem. Soc., Dalton Trans., 1976, 2484, J. Chem. Soc., Dalton Trans., 1981, 400, J. Chem. Soc., Dalton Trans., 1982, 1341, J. Organomet. Chem., 1986, 310, 255, Organometallics, 1990, 9, 2785, J. Am. Chem. Soc., 1996, 118, 11672, 1997, 119, 2950 |
| Библиографическая ссылка | H. Yasuda, K. Tatsumi, A. Nakamura, Acc. Chem. Res., 1985, 18, 120, and refs. therein |
| Библиографическая ссылка | J. A. Osborn, F. H. Jardine, J. F. Young, G. Wilkinson, J. T. Mague, G. Wilkinson, C. A. Tolman, P. Z. Meakin, D. L. Lindner, J. P. Jesson, H. L. M. van Gaal, F. L. A. van den Bekerom, Y. Ohtani, A. Yamagishi, M. Fujimoto, J. Chem. Soc. A, 1966, 1711, J. Chem. Soc. A, 1966, 1736, J. Am. Chem. Soc., 1974, 96, 2762, J. Organomet. Chem., 1977, 134, 237, Bull. Chem. Soc. Jpn., 1979, 52, 2149 |
| Библиографическая ссылка | T. Suzuki, Y. Tsuji, Y. Takegami, H. J. Harwood, Macromolecules, 1979, 12, 234 |
| Библиографическая ссылка | N. Ahmad, J. J. Levison, S. D. Robinson, M. F. Uttley, J. A. Osborn, G. Wilkinson, S. Arora, P. Binger, Inorg. Synth., 1974, 15, 58, Inorg. Synth., 1990, 28, 77, Synthesis, 1974, 801 |
| Библиографическая ссылка | S. Montelatici, A. van der Ent, J. A. Osborn, G. Wilkinson, J. Chem. Soc. A, 1968, 1054 |
