The isolation and structure of the novel cis-fused indolizidine 249h from frog skin: CIS- vs. trans-fused indolizidines distinguished by NMR

Heterocycles

Volumn 49, Issue 1, 1998, Pages 427-436

  Tokuyama, Takashi ^a   Shimada, Atsushi ^b   Martin Garraffo, H ^c   Spande, Thomas F ^a,b   Daly, John W ^c,d  

^a Osaka Prefecture University   (Japan)

^b Takara Shuzo Co Ltd ^*  (Japan)

^c TAKARA SHUZO CO LTD   (Japan)

^d NATIONAL INSTITUTE OF DIABETES AND DIGESTIVE AND KIDNEY DISEASES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

INDOLIZIDINE ALKALOID;

ARTICLE; CHEMICAL STRUCTURE; FROG; INFRARED SPECTROSCOPY; MASS SPECTROMETRY; NONHUMAN; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STRUCTURE ANALYSIS;

EID: 0032585380     PISSN: 03855414     EISSN: None     Source Type: Journal    
DOI: 10.3987/com-98-s61     Document Type: Article

References (28)

1. J.W. Daly, H.M. Garraffo, and T.F. Spande, 'The Alkaloids', Vol. 43, ed. by G.A. Cordell, Acad. Press, San Diego, 1993, p. 185.
2. J.W. Daly, H.M. Garraffo, and T.F. Spande, 'Alkaloids: Chemical and Biological Perspectives', Vol. 13, ed. by S.W. Pelletier, John Wiley and Sons, New York, 1999, p. 1.
3. H.M. Garraffo, P. Jain, T.F. Spande, and J.W. Daly, J. Nat. Prod., 1997, 60, 2.
4. Y. Takeuchi, P.J. Chivers, and T.A. Crabb, J. Chem. Soc., Chem. Commun., 1974, 216.;
5. G.V. Binst and D. Tourwe, Heterocycles, 1973, 1, 257.
6. T.A. Crabb, 'Ann. Reports on NMR Spectroscopy', Vol 6A, ed. by E.F. Mooney, Academic Press, London, 1975, p. 323.
7. The only other cis-fused simple indolizidine we are aware of is dendroprimine, 5R(5α,7α,9α)-5,7-dimethylindolizidine, where, as is the case with 249H, a severe steric interaction in the trans-fused conformation is relieved in adopting the cis-fused conformation. B. Liming and C. Lündin, Acta Chim. Scand., 1967, 21, 2136;
8. L. Blomqvist, K. Leander, B. Lüning, and J. Rosenblom, Acta Chim. Scand., 1972, 26, 3203.
9. Chem3D for the Macintosh computer (Cambridge Scientific Computing).
10. T. Tokuyama, T. Tsujita, A. Shimada, H.M. Garraffo, T.F. Spande, and J.W. Daly, Tetrahedron, 1991, 47, 5401.
11. T. Tokuyama, N. Nishimori, A. Shimada, M.W. Edwards, and J.W. Daly, Tetrahedron, 1987, 43, 643.
12. Enantioselective syntheses of 235B by R.P. Polniaszek and S.E. Belmont (J. Org. Chem., 1991, 56, 4868)
13. and Y. Shisido and C. Kibayashi (J. Org. Chem., 1992, 57, 2876) indicated that our originally proposed structure is probably enantiomeric to that of the natural material. Structure 2 is therefore represented as a mirror image of the originally proposed structure.
14. A.L. Smith, S.F. Williams, A.B. Holmes, L.R. Hughes, Z. Lidert, and C. Swithenbank, J. Am. Chem. Soc., 1988, 110, 8696.;
15. A.B. Holmes, A.L. Smith, S.F. Williams, L.R. Hughes, Z. Lidert, and C. Swithenbank, J. Org. Chem., 1991, 56, 1393.;
16. I. Collins, M.E. Fox, A.B. Holmes, S.F. Williams, R. Baker, I.J. Forbes, and M. Thompson, J. Chem. Soc., Perkin Trans. I, 1991, 175.
17. Alkaloid 263D. EIMS: m/z 263(6),
18. EIMS: M/z 248(2),
19. EIMS: M/z 234(10),
20. EIMS: M/z 229(2),
21. EIMS: M/z 180(100),
22. EIMS: M/z 178(11),
23. EIMS: M/z 164(10),
24. EIMS: M/z 150(3),
25. EIMS: M/z 148(3),
26. EIMS: M/z 136(4),
27. EIMS: M/z 124(13),
28. EIMS: M/z 109(3).