Easy access to various substituted 4-aminocyclopentenes by rearrangement of 2-ethenyl-substituted cyclopropylamines

Abstract

A variety of 2-ethenyl-substituted cyclopropylamines upon flash vacuum pyrolysis or under silver nitrate catalysis cleanly undergo ring enlargement and afford high yields (up to 95%) of 4-aminocyclopent-1-enes, some of which have unprecedented substitution patterns.

References

1. (a) D. Bouzard, P. Di Cesare, M. Essiz, J. P. Jacquet, P. Remuzon, A. Weber, T. Oki and M. Masuyoshi, J. Med. Chem., 1989, 32, 537; (b) A. Piergentili, P. Angeli, M. Giannella, M. Pigini, W. Quaglia and S. K. Tayebati, Arzneim. Forsch., 1996, 46, 99; (c) D. F. Morrow, P. C. Johnson, H. Torabi, D. Williams, D. L. Wedding, J. W. Craig and R. F. Majewski, J. Med. Chem., 1973, 16, 736; (d) S. Kamata, N. Haga, T. Tsuri, K. Uchida, H. Kakushi, H. Arita and K. Hanasaki, J. Med. Chem., 1990, 33, 299; (e) D. P. Curran, S. A. Gothe and S.-M. Choi, Heterocycles, 1993, 35, 1371.
2. (a) K. C. Murdock and R. B. Angier, J. Org. Chem., 1962, 27, 3317; (b) R. D. Elliot, G. A. Rener, J. M. Riordan, J. A. Secrist III, L. L. Bennett, Jr., W. B. Parker and J. A. Montgomery, J. Med. Chem., 1994, 37, 739; (c) M. Koga and S. W. Schneller, Tetrahedron Lett., 1990, 31, 5861; (d) K. C. Murdock and R. B. Angier, Tetrahedron Lett., 1962, 415; (e) J. Béres, Gy. Sági, I. Tömösközi, L. Gruber, E. Baitz-Gács, L. Ötvös and E. De Clercq, J. Med. Chem., 1990, 33, 1353; (f) M. Legraverend, C. Huel, J. Guilhem and E. Bisagni, Carbohydr. Res., 1992, 228, 21; (g) F. Girard, C. Demaison, M.-G. Lee and L. A. Agrofoglio, Tetrahedron, 1998, 54, 8745.
3. (a) K. C. Murdock and R. B. Angier, J. Org. Chem., 1962, 27, 2395; (b) K. Hammer and K. Undheim, Tetrahedron, 1997, 53, 2309.
4. T. Hudlicky, D. A. Becker, R. L. Fan and S. Kozhushkov, in Methods of Organic Chemistry(Houben-Weyl), ed. A. de Meijere, Thieme, Stuttgart, 1997, vol. E 17c, p. 2538.
5. (a) C. M. Williams, V. Chaplinski, P. R. Schreiner and A. de Meijere, Tetrahedron Lett., 1998, 39, 7695; (b) A. de Meijere, A. Kourdioukov, V. Chaplinski, M. Kordes and C. M. Williams, unpublished work.
6. H. G. Richey, Jr. and D. W. Shull, Tetrahedron Lett., 1976, 575.
7. Even higher temperatures resulted in decomposition and lower temperatures afforded more starting material.
8. H. M. Frey and R. K. Solly, J. Chem. Soc. (B), 1970, 996.
9. (a) J. M. Simpson and H. G. Richey, Tetrahedron Lett., 1973, 2545; (b) G. McGaffin, B. Grimm, U. Heinicke, H. Michaelsen, A. de Meijere and R. Walsh, unpublished work.
10. L. J. Morris, Chem. Ind., 1962, 1239 ; silica gel [200 g] was suspended in acetonitrile [∼400 ml] to which was added a solution of silver nitrate [40 g] in acetonitrile [∼50 ml]. The solvent was then slowly evaporated [1 Torr] and the silica gel placed in an oven [80 °C] or in an evacuated flask [0.01 Torr] for 24 h.