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DOI: 10.1039/A709126E (Paper) Reference Section for: Chem. Commun., 1998, 999-1000

Novel mechanistic proposal for the Dötz reaction derived from a density functional study: the chromahexatriene route

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Maricel Torrent

Abstract

A new mechanism for the Dötz reaction of vinylcarbene complexes with ethyne proceeds through a chromahexatriene intermediate instead of a vinylketene with smooth energy changes and low energy barriers.

References

  1. K. H. Dötz, Angew. Chem., Int. Ed. Engl., 1975, 14, 644 CrossRef.
  2. K. H. Dötz, Angew. Chem., Int. Ed. Engl., 1984, 23, 587 CrossRef.
  3. C. P. Casey, in Reactive Intermediates, ed. M. Jones, Jr., and R. A. Moss, Wiley, New York, 1981, vol. 2, p. 155 Search PubMed.
  4. J. Barluenga, F. Aznar, A. Martín, S. García-Granda and E. Pérez-Carreño, J. Am. Chem. Soc., 1994, 116, 11 191 CrossRef CAS.
  5. E. Chelain, R. Goumont, L. Hamon, A. Parlier, M. Rudler, H. Rudler, J. C. Daran and J. Vaissermann, J. Am. Chem. Soc., 1992, 114, 8088 CrossRef CAS; B. A. Anderson, J. Bao, T. A. Brandvold, C. A. Challener, W. D. Wulff, Y.-C. Xu and A. L. Rheingold, J. Am. Chem. Soc., 1993, 115, 10671 CrossRef CAS.
  6. P. Hofmann and M. Hämmerle, Angew. Chem., Int. Ed. Engl., 1989, 28, 908 CrossRef; P. Hofmann, M. Hämmerle and G. Unfried, New J. Chem., 1991, 15, 769 Search PubMed.
  7. M. M. Gleichmann, K. H. Dötz and B. A. Hess, J. Am. Chem. Soc., 1996, 118, 10 551 CrossRef CAS.
  8. H. Fischer, J. Mühlemeier, R. Märkl and K. H. Dötz, Chem. Ber., 1982, 115, 1355 CAS.
  9. GAUSSIAN 94, Gaussian, Inc. Pittsburg PA, 1995.
  10. A. D. Becke, Phys. Rev., 1988, A38, 3098 Search PubMed; J. P. Perdew, Phys. Rev., 1986, B33, 8822 Search PubMed; ibid., 1986, B34, 7406E Search PubMed.
  11. H. B. Schlegel, J. Comput. Chem., 1982, 3, 214 CrossRef CAS.
  12. The 6-31G** basis set13 was employed for C, O and H atoms. For the chromium atom we used a basis set as described by Wachters14 in a (62111111/3312/311) contraction scheme.
  13. J. S. Binkley, J. A. Pople and W. J. Hehre, J. Am. Chem. Soc., 1980, 102, 939 CrossRef CAS.
  14. A. J. H. Wachters, J. Chem. Phys., 1970, 52, 1033 CrossRef CAS.
  15. F. Zaera, Chem. Rev., 1995, 95, 2651 CrossRef CAS.
  16. C. P. Casey, A. J. Shusterman, N. W. Vollendorf and K. J. Haller, J. Am. Chem. Soc., 1982, 104, 2417 CrossRef CAS.
  17. M. J. McGeary, T. L. Tonker and J. L. Templeton, Organometallics, 1985, 4, 2102 CrossRef CAS.
  18. K. H. Dötz, T. Schäfer, F. Kroll and K. Harms, Angew. Chem., Int. Ed. Engl., 1992, 31, 1236 CrossRef.
  19. K. H. Dötz, M. Popall and G. Müller, J. Org. Chem., 1987, 334, 57.
  20. F. Hohmann, S. Siemoneit, M. Nieger, S. Kotila and K. H. Dötz, Chem. Eur. J., 1997, 3, 853 CAS.
  21. T. R. Tritcak, J. B. Sheridan, M. L. Cote, R. A. Lalancette and J. P. Rose, J. Chem. Soc., Dalton Trans., 1995, 6, 931 RSC.
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