A novel route to (±)-aspidospermidine: First application of 'radical- polar crossover' reactions to total synthesis

Tetrahedron Letters

Volumn 40, Issue 1, 1999, Pages 161-164

  Callaghan, Owen ^a   Lampard, Christopher ^a,b   Kennedy, Alan R ^a   Murphy, John A ^a  

^a UNIVERSITY OF STRATHCLYDE   (United Kingdom)

^b ASTRAZENECA   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID; ASPIDOSPERMIDINE; DIAZONIUM COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0032888938     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)80047-6     Document Type: Article

References (29)

1. Previous syntheses of aspidospermidine: A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637. T. Gallagher, P. Magnus and J. C. Huffman, J. Am. Chem. Soc., 1983, 705, 4750. S. B. Mandai, V. S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236. P. Le Ménez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915. D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292. P. Forns, A. Diaz and M. Rubiralta, J. Org. Chem., 1996, 61, 7882.
2. Previous syntheses of aspidospermidine: A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637. T. Gallagher, P. Magnus and J. C. Huffman, J. Am. Chem. Soc., 1983, 705, 4750. S. B. Mandai, V. S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236. P. Le Ménez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915. D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292. P. Forns, A. Diaz and M. Rubiralta, J. Org. Chem., 1996, 61, 7882.
3. Previous syntheses of aspidospermidine: A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637. T. Gallagher, P. Magnus and J. C. Huffman, J. Am. Chem. Soc., 1983, 705, 4750. S. B. Mandai, V. S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236. P. Le Ménez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915. D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292. P. Forns, A. Diaz and M. Rubiralta, J. Org. Chem., 1996, 61, 7882.
4. Previous syntheses of aspidospermidine: A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637. T. Gallagher, P. Magnus and J. C. Huffman, J. Am. Chem. Soc., 1983, 705, 4750. S. B. Mandai, V. S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236. P. Le Ménez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915. D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292. P. Forns, A. Diaz and M. Rubiralta, J. Org. Chem., 1996, 61, 7882.
5. Previous syntheses of aspidospermidine: A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637. T. Gallagher, P. Magnus and J. C. Huffman, J. Am. Chem. Soc., 1983, 705, 4750. S. B. Mandai, V. S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236. P. Le Ménez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915. D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292. P. Forns, A. Diaz and M. Rubiralta, J. Org. Chem., 1996, 61, 7882.
6. Previous syntheses of aspidospermidine: A. Camerman, N. Camerman, J. P. Kutney, E. Piers and J. Trotter, Tetrahedron Lett., 1965, 637. T. Gallagher, P. Magnus and J. C. Huffman, J. Am. Chem. Soc., 1983, 705, 4750. S. B. Mandai, V. S. Giri, M. S. Sabeena and S. C. Pakrashi, J. Org. Chem., 1988, 53, 4236. P. Le Ménez, N. Kunesch, S. Liu and E. Wenkert, J. Org. Chem., 1991, 56, 2915. D. Desmaële and J. d'Angelo, J. Org. Chem., 1994, 59, 2292. P. Forns, A. Diaz and M. Rubiralta, J. Org. Chem., 1996, 61, 7882.
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11. For an alternative method, see V. F. Patel and G. Pattenden, J. Chem. Soc., Perkin Trans, 1, 1990, 2703. H. Bhandal, V. F. Patel, G. Pattenden and J. J. Russell, J. Chem. Soc., Perkin Trans, 1, 1990, 2691.
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20. Crystal data for (17). Monoclinic, C2/c, colourless crystal, a = 32.972(5), b = 11.611(4), c = 11.161(5), β = 108.51(2), V = 4046(2), z = 8, R = 0.059, GOF = 1.54.
21. For related studies, see: A. Azzouzi, B. Perrin, M.-E. Sinibaldi, J.-C. Gramain and C. Lavaud, Tetrahedron Lett., 1993, 34, 5451. A. Azzouzi, B. Perrin, M.E. Sinibaldi, D. Gardette, C. Lavaud, D. Vallée-Goyet, J.-C. Gramain, A. Kerbal, Bull. Soc. Chim. Fr., 1995, 132, 681.
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23. This is in line with modelling studies which show that the cyclohexyl ring in the most stable conformer of (14) adopts a boat conformation, but inverted with respect to that of (18). Approach to the lower face of the ketone in (14) is impeded by H§.
24. E. Piers and J. Renaud, J. Org. Chem., 1993, 58, 11.
25. M. E. Kuehne, T. Wang and P. J. Seaton, J. Org. Chem., 1996, 61, 6001.
26. 18 of stereochemistry.
27. C. Y. Hong, N. Kado and L. E.Overman, J. Amer. Chem. Soc. 1993 115, 11028.
28. K. A. Parker and D. Fokas, J. Amer. Chem. Soc. 1993, 114, 9688; J. Org. Chem., 1994, 59, 3933.
29. K. A. Parker and D. Fokas, J. Amer. Chem. Soc. 1993, 114, 9688; J. Org. Chem., 1994, 59, 3933.