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DOI: 10.1039/A808147F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1999, 509-512

One-pot stereoselective synthesis of trifluoromethylated penta-(2Z,4E[hair space])-dienenitriles via double olefination

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Yanchang Shen, Jiahong Ni, Ping Li and Jie Sun

Abstract

A novel double olefination via sequential transformation of diethyl (1-cyanoethyl)phosphonate and its application to the synthesis of substituted trifluoromethylated pentadienenitriles with 2Z,4E-isomers formed exclusively in 71–85% yield are described. This reaction is of broad scope since R may be alkyl, aryl or a heterocyclic group. The configuration of the products was ascertained on the basis of X-ray crystallographic analysis. The stereochemical results are rationalized by the proposed mechanism.

References

  1. K. A. Reynolds, P. G. Dopico, M. S. Brody and M. G. Finn, J. Org. Chem., 1997, 62, 2564 CrossRef CAS.
  2. K. A. Reynolds, P. G. Dopico, M. J. Sundermann, K. A. Hughes and M. G. Finn, J. Org. Chem., 1993, 58, 1298 CrossRef CAS.
  3. (a) L. F. Tietze and U. Beifuss, Angew. Chem., Int. Ed. Engl., 1993, 32, 131 CrossRef; (b) A. Padwa, E. A. Curtis and V. P. Sandanayaka, J. Org. Chem., 1996, 61, 73 CrossRef CAS; (c) L. F. Tietze, Chem. Rev., 1996, 96, 115 CrossRef CAS; (d) P. J. Parsons, C. S. Penkett and A. J. Shell, Chem. Rev., 1996, 96, 195 CrossRef CAS.
  4. Y. Shen and J. Ni, (a)J. Org. Chem., 1997, 62, 7260. (b)J. Chem. Res. (S), 1997, 358; J. Fluorine Chem., (c), 1997, 86, 173; (d) 1998, 89, 141 Search PubMed.
  5. (a) J. T. Welch, Tetrahedron, 1987, 43, 3123 CrossRef CAS; (b) J. T. Welch and S. Eswarakrishnam, Fluorine in Biorganic Chemistry, Wiley, New York, 1991 Search PubMed; (c) G. Resnati, Tetrahedron, 1993, 49, 9385 CrossRef CAS; (d) Organofiuorine Compounds in Medicinal Chemistry and Biomedical Applications, ed. R. Filler, Y. Kobayashi and L. M. Yagupolski, Elsevier, Amsterdam, 1993 Search PubMed; (e) Inventory of Industrial Flurobiochemicals, ed. A. Becker, Eyrolles, Paris, 1996 Search PubMed.
  6. Y. Morisawa, A. Yasuda and K. Uchida, Jpn. Kokai Tokkyo Koho JP, 02 270 893 [90, 270 893](CL. C07H19/073)(Chem. Abstr., 1991, 115, 143939w) Search PubMed.
  7. (a) A. J. J. Van Den Berg, S. F. A. J. Horsten, J. J. K. Van Den Bosch, B. H. Kroes and R. P. Labadie, Phytochemistry, 1995, 40, 597 CrossRef; (b) M. Yoshikawa, H. Shimada, H. Shimoda, H. Matsuda, J. Yamahara and N. Murakami, Chem. Pharm. Bull., 1995, 43, 1245 CAS.
  8. (a) M. A. McClinton and D. A. McClinton, Tetrahedron, 1992, 48, 6555 CrossRef CAS; (b) G. K. S. Prakash and A. K. Yudin, Chem. Rev., 1997, 97, 757 CrossRef CAS.
  9. W. Perlikowska, M. J. Mphahlele and T. A. Modro, J. Chem. Soc., Perkin Trans. 2, 1997, 967 RSC.
  10. R. N. Gedye, K. C. Westaway, P. Arora, R. Bisson and A. H. Khalil, Can. J. Chem., 1977, 55, 1218 CAS It was reported in this paper that space-filling models indicated that the steric hindrance between the CH3 group and the CO2CH3 group was larger than that between the CH2P (O)(OEt)2 group and the CO2CH3 group.
  11. H.-J. Tasi, A. Thenappan and D. J. Burton, J. Org. Chem., 1994, 59, 7085 CrossRef.
  12. M. L. Raggio and D. S. Watt, J. Org. Chem., 1976, 41, 1873 CrossRef CAS.
  13. G. M. Sheldrick, SHELXS-86 in Crystallographic Computing 3, ed. G. M. Sheldrick, C. Kruger and R. Goddard, Oxford University Press, 1985, pp. 175–189 Search PubMed.
  14. P. T. Beurskens, G. Admiraal, G. Beurskens, W. P. Bosman, S. Garcia-Granda, R. O. Gould, J. M. M. Smits and C. Smykalla, DIRDIF-92, University of Nijmegen, The Netherlands, 1992.
  15. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, The Woodlands, TX, 1985 and 1992.
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