New approach to the progesterone BCD-ring system by utilizing a tandem transannular radical cyclization

Tetrahedron Letters

Volumn 40, Issue 12, 1999, Pages 2363-2366

  Tomida, Satoshi ^a   Doi, Takayuki ^a   Takahashi, Takashi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Molecular modelling mechanics; Radicals and radical reactions; Steroids and sterols; Transannular reactions

Indexed keywords

PROGESTERONE; RADICAL;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; MECHANICS; MOLECULAR MODEL; PROGESTERONE SYNTHESIS; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY;

EID: 0033583301     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00187-2     Document Type: Article

References (29)

1. 1. For a review, see: Still, W. C. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 233; Takahashi, T. In Studies in Natural Product Chemistry; Rahman, A.-U., Ed.; Elsevier Science Publishers B. V.: Amsterdam, 1991; Vol. 8, p 175.
2. 1. For a review, see: Still, W. C. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 233; Takahashi, T. In Studies in Natural Product Chemistry; Rahman, A.-U., Ed.; Elsevier Science Publishers B. V.: Amsterdam, 1991; Vol. 8, p 175.
3. 2. Takahashi, T.; Shimizu, K.; Doi, T.; Tsuji, J.; Fukazawa, Y. J. Am. Chem. Soc. 1988, 110, 2674-2676; Takahashi, T.;Sakamoto, Y.; Doi, T. Tetrahedron Lett. 1992, 33, 3519-3522.
4. 2. Takahashi, T.; Shimizu, K.; Doi, T.; Tsuji, J.; Fukazawa, Y. J. Am. Chem. Soc. 1988, 110, 2674-2676; Takahashi, T.; Sakamoto, Y.; Doi, T. Tetrahedron Lett. 1992, 33, 3519-3522.
5. 3. Deslongchamps, P. Aldrichim. Acta 1984, 17, 59.
6. 4. For recent reviews, see: Stork, G. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 359; Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: Oxford, 1986; Jasperse, C. P.;Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237-1286; Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon: Oxford, 1991; Vol. 4, p 779; Curran, D. P.; Porter, N. A.;Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1995.
7. 4. For recent reviews, see: Stork, G. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 359; Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: Oxford, 1986; Jasperse, C. P.;Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237-1286; Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon: Oxford, 1991; Vol. 4, p 779; Curran, D. P.; Porter, N. A.;Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1995.
8. 4. For recent reviews, see: Stork, G. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 359; Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: Oxford, 1986; Jasperse, C. P.; Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237-1286; Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon: Oxford, 1991; Vol. 4, p 779; Curran, D. P.; Porter, N. A.;Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1995.
9. 4. For recent reviews, see: Stork, G. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 359; Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: Oxford, 1986; Jasperse, C. P.;Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237-1286; Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon: Oxford, 1991; Vol. 4, p 779; Curran, D. P.; Porter, N. A.;Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1995.
10. 4. For recent reviews, see: Stork, G. In Current Trends in Organic Synthesis; Nozaki, H., Ed.; Pergamon: Oxford, 1983; p 359; Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: Oxford, 1986; Jasperse, C. P.;Curran, D. P.; Fevig, T. L. Chem. Rev. 1991, 91, 1237-1286; Curran, D. P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Semmelhack, M. F., Eds.; Pergamon: Oxford, 1991; Vol. 4, p 779; Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, 1995.
11. 5. (a) Takahashi, T.; Katouda, W.; Sakamoto, Y.; Tomida, S.; Yamada, H. Tetrahedron Lett. 1995, 36, 2273-2276;
12. (b) Takahashi, T.; Tomida, S.; Sakamoto, Y.; Yamada, H. J. Org. Chem. 1997, 62, 1912-1913 and references therein.
13. 6. Myers, A. G.; Condroski, K. R. J. Am. Chem. Soc. 1995, 117, 3057-3083.
14. 7. For a review, see: Handa, S.; Pattenden, G. Contem. Org. Synth. 1997, 4, 196-215. For synthetic approaches for steroid skeleton, see: Begley, M. J.; Pattenden, G.; Smithies, A. J.; Walter, D. S. Tetrahedron Lett. 1994, 35, 2417-2420; Jahn, U.; Curran, D. P. Tetrahedron Lett. 1995, 36, 8921-8924; Jones, P.; Pattenden, G. Synlett 1997, 398-400; Pattenden, G.;Wiedenau, P. Tetrahedron Lett. 1997, 38, 3647-3650.
15. 7. For a review, see: Handa, S.; Pattenden, G. Contem. Org. Synth. 1997, 4, 196-215. For synthetic approaches for steroidskeleton, see: Begley, M. J.; Pattenden, G.; Smithies, A. J.; Walter, D. S. Tetrahedron Lett. 1994, 35, 2417-2420; Jahn, U.; Curran, D. P. Tetrahedron Lett. 1995, 36, 8921-8924; Jones, P.; Pattenden, G. Synlett 1997, 398-400; Pattenden, G.;Wiedenau, P. Tetrahedron Lett. 1997, 38, 3647-3650.
16. 7. For a review, see: Handa, S.; Pattenden, G. Contem. Org. Synth. 1997, 4, 196-215. For synthetic approaches for steroidskeleton, see: Begley, M. J.; Pattenden, G.; Smithies, A. J.; Walter, D. S. Tetrahedron Lett. 1994, 35, 2417-2420; Jahn, U.; Curran, D. P. Tetrahedron Lett. 1995, 36, 8921-8924; Jones, P.; Pattenden, G. Synlett 1997, 398-400; Pattenden, G.;Wiedenau, P. Tetrahedron Lett. 1997, 38, 3647-3650.
17. 7. For a review, see: Handa, S.; Pattenden, G. Contem. Org. Synth. 1997, 4, 196-215. For synthetic approaches for steroidskeleton, see: Begley, M. J.; Pattenden, G.; Smithies, A. J.; Walter, D. S. Tetrahedron Lett. 1994, 35, 2417-2420; Jahn, U.; Curran, D. P. Tetrahedron Lett. 1995, 36, 8921-8924; Jones, P.; Pattenden, G. Synlett 1997, 398-400; Pattenden, G.;Wiedenau, P. Tetrahedron Lett. 1997, 38, 3647-3650.
18. 7. For a review, see: Handa, S.; Pattenden, G. Contem. Org. Synth. 1997, 4, 196-215. For synthetic approaches for steroidskeleton, see: Begley, M. J.; Pattenden, G.; Smithies, A. J.; Walter, D. S. Tetrahedron Lett. 1994, 35, 2417-2420; Jahn, U.; Curran, D. P. Tetrahedron Lett. 1995, 36, 8921-8924; Jones, P.; Pattenden, G. Synlett 1997, 398-400; Pattenden, G.; Wiedenau, P. Tetrahedron Lett. 1997, 38, 3647-3650.
19. 8. Rubin, M. B. Steroids 1963, 2, 561-581.
20. 9. Burkert, U.; Allinger, N. L. Molecular Mechanics: ACS: Washington, DC, 1982; Houk, K. N.; Paddon-Row, M. N.;Rondan, N. G.; Wu. Y.-D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108-1117; Eksterowicz, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439-2461.
21. 9. Burkert, U.; Allinger, N. L. Molecular Mechanics: ACS: Washington, DC, 1982; Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu. Y.-D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108-1117; Eksterowicz, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439-2461.
22. 9. Burkert, U.; Allinger, N. L. Molecular Mechanics: ACS: Washington, DC, 1982; Houk, K. N.; Paddon-Row, M. N.;Rondan, N. G.; Wu. Y.-D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108-1117; Eksterowicz, J. E.; Houk, K. N. Chem. Rev. 1993, 93, 2439-2461.
23. 10. All calculations were performed on MACROMODEL/BATCHMIN (ver 5.5). We are grateful to Professor W.C. Still for providing a copy of this program. Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Lipton, M.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440-467.
24. 11. Spellmeyer, D. C.; Houk, K. N. J. Org. Chem. 1987, 52, 959-974.
25. -1.
26. 13. Cyclized Product 4b was obtained with an 88 : 12 mixture of the 10α-and 10β-methyl group. Neither 6b and cis-isomer (13-Me/14-H) was detected (less than 5%).
27. 14. The radical cyclization of 17α-11 gave a 43 : 57 mixture of 4a and 6a in 94% combined yield. The 6a isomerized to 17β-isomer, which was identical with the synthetic material previously reported; Uskokovic, M.; Iacobelli, J.; Philion, R.; Williams, T. J. Am. Chem. Soc. 1966, 88, 4538-4539; Uskokovic, M. R.; Williams, T. H. U.S. Patent 3,956,316, 1973 to Hoffmann-La Roche Inc.
28. 14. The radical cyclization of 17α-11 gave a 43 : 57 mixture of 4a and 6a in 94% combined yield. The 6a isomerized to 17β-isomer, which was identical with the synthetic material previously reported; Uskokovic, M.; Iacobelli, J.; Philion, R.;Williams, T. J. Am. Chem. Soc. 1966, 88, 4538-4539; Uskokovic, M. R.; Williams, T. H. U.S. Patent 3,956,316, 1973 to Hoffmann-La Roche Inc.
29. 15. The authors have deposited atomic coordinates for the 10α-methyl 5b with the Cambridge Crystallographic Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.