Vicinal diamination of 1,4-dihydropyridines

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Rodolfo Lavilla, Rakesh Kumar, Oscar Coll, Carme Masdeu and Joan Bosch


Abstract

Electrophilic interaction of iodine with N-alkyl-1,4-dihydropyridines 1 in the presence of secondary amines stereoselectively leads to the corresponding trans-2,3-diamino-1,2,3,4-tetrahydropyridines 2 in satisfactory yields (79–94%); the method allows the synthesis of piperidine, pyrrolidine, morpholine and piperazine derivatives.


References

  1. For a review on the chemistry of dihydropyridines, see: D. M. Stout and A. I. Meyers, Chem. Rev., 1982, 82, 223 Search PubMed.
  2. R. Lavilla, F. Gullón, X. Barón and J. Bosch, Chem. Commun., 1997, 213 RSC.
  3. R. Lavilla, O. Coll, R. Kumar and J. Bosch, J. Org. Chem., 1998, 63, 2728 CrossRef CAS.
  4. R. Lavilla, O. Coll, M. Nicolàs and J. Bosch, Tetrahedron Lett., 1998, 39, 5089 CrossRef CAS.
  5. For the aziridination of 1,4-dihydropyridines, see: B. K. Warren and E. E. Knaus, J. Med. Chem., 1981, 24, 462 Search PubMed; For a review on the chemistry of aminals, see: L. Duhamel in The Chemistry of Functional Groups, Supplement F, Part 2, ed. S. Patai, Wiley, New York, 1982, p. 849 CrossRef CAS.
  6. For a general review of olefin amination reactions promoted by electrophiles, see: M. Orena, in Methods of Organic Chemistry, Stereoselective Synthesis, ed. G. Helmchen, R. W. Hoffmann, J. Mulzer and E. Schaumann, Thieme, Stuttgart, 1996, vol. 9. p. 5291 Search PubMedAlso see: J. Rodriguez and J.-P. Dulcère, Synthesis, 1993, 1177 Search PubMed.
  7. Only intramolecular haloamination of olefins is relevant in synthesis: D. R. Williams, D. L. Brown and J. M. Benbow, J. Am. Chem. Soc., 1989, 111, 1923 Search PubMed; S. R. Wilson, S. R. Sawicki and J. C. Huffman, J. Org. Chem., 1981, 46, 3887 CrossRef CAS; I. Monkovic, T. T. Conway, H. Wong, Y. G. Perron, I. J. Pachter and B. Belleau, J. Am. Chem. Soc., 1973, 95, 7910 CrossRef CAS; D. Tanner, M. Sellén and J. E. Bäckvall, J. Org. Chem., 1989, 54, 3374 CrossRef CAS; W. R. Bowman, D. L. Clark and R. J. Marmon, Tetrahedron, 1994, 50, 1275 CrossRef CAS.
  8. For the preparation of N-alkyl-1,4-dihydropyridines, see: M. E. Brewster, A. Simay, K. Czako, D. Winwood, H. Farag and N. Bodor, J. Org. Chem., 1989, 54, 3721 Search PubMed.
  9. For a related regio- and stereo-selective ring opening of aziridinium ions, see: S. E. de Sousa and P. O'Brien, Tetrahedron Lett., 1997, 38, 4885 Search PubMed.
  10. For a recent and effective method to carry out this transformation, see: J. Du Bois, C. S. Tomooka, J. Hong and E. M. Carreira, J. Am. Chem. Soc., 1997, 119, 3179 Search PubMed; Also see: M. SunoseK. M. AndersonA. G. OrpenT. GallagherS. J. F. MacdonaldTetrahedron Lett., in the press CrossRef CAS.
  11. E. J. Corey, S. Sarshar, M. D. Azimioara, R. C. Newbold and M. C. Noe, J. Am. Chem. Soc., 1996, 118, 7851 CrossRef CAS.
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