First structurally defined catalyst for the asymmetric addition of trimethylsilyl cyanide to benzaldehyde

(Note: The full text of this document is currently only available in the PDF Version )

Michael North, Charles Orizu, Vitali I. Tararov, Nicolai S. Ikonnikov, Yuri N. Belokon, David E. Hibbs, Michael B. Hursthouse and K. M. Abdul Malik


Abstract

Titanium complex TiCl2L [H2L = (R,R)-N,N′-bis(3,5-di-tert-butylsalicylidene)hexane-1,2-diamine] 2 has been prepared, characterised by X-ray crystallography and shown to be an active catalyst for the asymmetric addition of Me3SiCN to benzaldehyde, producing (S)-2-phenyl-2-trimethylsilyloxyacetonitrile in 86% ee at room temperature.


References

  1. C. G. Kruse, in Chirality in Industry, ed. A. N. Collins, G. N. Sheldrake and J. Crosby, Wiley, Chichester, 1992, ch. 14 Search PubMed.
  2. M. North, Synlett, 1993, 807 CrossRef CAS; F. Effenberger, Angew. Chem., Int. Ed. Engl., 1994, 33, 1555 CrossRef; M. North, in Comprehensive Organic Functional Group Transformations, ed. A. R. Katritzky, O. Meth-Cohn, C. W. Rees and G. Pattenden, Pergamon, Oxford, 1995, vol. 3, ch. 18 Search PubMed.
  3. Y. Belokon', N. Ikonnikov, M. Moscalenko, M. North, S. Orlova, V. Tararov and L. Yashkina, Tetrahedron: Asymmetry, 1996, 7, 851 CrossRef CAS; Y. Belokon', M. Flego, N. Ikonnikov, M. Moscalenko, M. North, C. Orizu, V. Tararov and M. Tasinazzo, J. Chem. Soc., Perkin Trans. 1, 1997, 1293 RSC.
  4. A. Abiko and G.-q. Wang, J. Org. Chem., 1996, 61, 2264 CrossRef CAS See also the references cited in refs. 2 and 3.
  5. Y. Belokon', N. Ikonnikov, M. North, C. Orizu and V. Tararov, unpublished results.
  6. J. F. Larrow, E. N. Jacobsen, Y. Gao, Y. Hong, X. Nie and C. Zepp, J. Org. Chem., 1994, 59, 1939 CrossRef CAS and references cited therein.
  7. G. Gilli, D. W. J. Cruickshank, R. L. Beddoes and O. S. Mills, Acta. Crystallogr., Sect. B, 1972, 28, 1889 CrossRef CAS; M. Pasquali, F. Marchetti, A. Landi and C. Floriani, J. Chem. Soc., Dalton Trans., 1978, 545 RSC; C. Floriani, E. Solari, F. Corazza, A. Chiesi-Villa and C. Guastini, Angew. Chem., Int. Ed. Engl., 1989, 28, 64 CrossRef; E. Solari, C. Floriani, A. Chiesi-Villa and C. Rizzoli, J. Chem. Soc. Dalton Trans., 1992, 367 RSC; F. Franceschi, E. Gallo, E. Solari, C. Floriani, A. Chiesi-Villa, C. Rizzoli, N. Re and A. Sgamell, Chem. Eur. J., 1996, 2, 1466 CrossRef CAS; T. Repo, M. Klinga, M. Leskela, P. Pietikainen and G. Brunow, Acta. Crystallgr., Sect. C., 1996, 52, 2742 CrossRef; E. Gallo, E. Solari, F. Franceschi, C. Floriani, A. Chiesi-Villa and C. Rizzoli, Inorg. Chem., 1995, 34, 2495 CrossRef CAS.
  8. K. M. Carroll, J. Schwartz and D. M. Ho, Inorg. Chem., 1994, 33, 2707 CrossRef CAS.
  9. For dimeric and polymeric chiral (salen)titanium complexes, see K. Nakajima, C. Sasaki, M. Kojima, T. Aoyama, S. Ohba, Y. Saito and J. Fujita, Chem. Lett., 1987, 2189 Search PubMed; T. Aoyama, S. Ohba, Y. Saito, C. Sasaki, M. Kojima, J. Fujita and K. Nakajima, Acta. Crystallogr., Sect. C, 1988, 44, 1309 CAS; A. Kless, C. Lefeber, A. Spannenberg, R. Kempe, W. Baumann, J. Holz and A. Börner, Tetrahedron, 1996, 52, 14 599 CrossRef.
  10. G. M. Sheldrick, Acta. Crystallogr., 1990, A46, 467 CrossRef CAS.
  11. J. A. Darr, S. R. Drake, M. B. Hursthouse and K. M. A. Malik, Inorg. Chem., 1993, 32, 5704 CrossRef CAS.
  12. G. M. Sheldrick, ‘SHELXL93: Program for Crystal Structure Refinement’, University of Gottingen, Germany, 1993.
Click here to see how this site uses Cookies. View our privacy policy here.