Stereoselective synthesis of steroids with the heck reaction

Angewandte Chemie (International Edition in English)

Volumn 35, Issue 19, 1996, Pages 2259-2261

  Tietze, Lutz F ^a   Nobel, Thomas ^a   Spescha, Maurus ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

Domino reactions; Estrones; Heck reactions; Steroids; Synthetic methods

Indexed keywords

EID: 0030459150     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199622591     Document Type: Article

References (37)

1. F. J. Zeelen, Nat. Prod. Rep. 1994, 11, 607.
2. Reviews: E. Negishi, C. Coperet, S. Ma, S. Liou, F. Liu, Chem. Rev. 1996, 96, 365; W. Cabri, I. Candiani, Acc. Chem. Res. 1995, 28, 2; A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379. R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985.
3. Reviews: E. Negishi, C. Coperet, S. Ma, S. Liou, F. Liu, Chem. Rev. 1996, 96, 365; W. Cabri, I. Candiani, Acc. Chem. Res. 1995, 28, 2; A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379. R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985.
4. Reviews: E. Negishi, C. Coperet, S. Ma, S. Liou, F. Liu, Chem. Rev. 1996, 96, 365; W. Cabri, I. Candiani, Acc. Chem. Res. 1995, 28, 2; A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379. R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985.
5. Reviews: E. Negishi, C. Coperet, S. Ma, S. Liou, F. Liu, Chem. Rev. 1996, 96, 365; W. Cabri, I. Candiani, Acc. Chem. Res. 1995, 28, 2; A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379. R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985.
6. Reviews: E. Negishi, C. Coperet, S. Ma, S. Liou, F. Liu, Chem. Rev. 1996, 96, 365; W. Cabri, I. Candiani, Acc. Chem. Res. 1995, 28, 2; A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379. R. F. Heck, Palladium Reagents in Organic Synthesis, Academic Press, London, 1985.
7. a) T. Mandai, T. Matsumoto, M. Kawada, J. Tsuji, Tetrahedron 1994, 49, 5483;
8. b) L. F. Tietze, P. S. V. Subba Rao, Synlett 1993, 291.
9. Z. G. Hajos, D. R. Parrish, J. Org. Chem. 1974, 39, 1615; U. Eder, G. Sauer, R. Wiechert. Angew. Chem. 1971, 83, 492; Angew. Chem. Int. Ed. Engl. 1971, 10, 496.
10. Z. G. Hajos, D. R. Parrish, J. Org. Chem. 1974, 39, 1615; U. Eder, G. Sauer, R. Wiechert. Angew. Chem. 1971, 83, 492; Angew. Chem. Int. Ed. Engl. 1971, 10, 496.
11. Z. G. Hajos, D. R. Parrish, J. Org. Chem. 1974, 39, 1615; U. Eder, G. Sauer, R. Wiechert. Angew. Chem. 1971, 83, 492; Angew. Chem. Int. Ed. Engl. 1971, 10, 496.
12. a) R. C. Larock, W. H. Gong. J. Org. Chem. 1989, 54, 2047;
13. b) R. C. Larock, B. E. Baker, Tetrahedron Lett. 1988, 29, 905;
14. c) T. Jeffery, ibid. 1985, 26, 2667.
15. 4NCl, 2.0 equiv 5a, DMF, 80°C, 80h.
16. 3, 2.0 equiv 5a, DMF, 110°C, 60h.
17. 4NCl. 2.0 equiv 5b, DMF, 90°C. 43h.
18. 4,2.0 equiv 5 b, DMF, 90°C, 64h; 6b: 7b 2/1.
19. L. F. Tietze, R. Schimpf, Chem. Ber. 1994, 127, 2235; Angew. Chem. Int. Ed. Engl. 1994, 33, 1089.
20. L. F. Tietze, R. Schimpf, Chem. Ber. 1994, 127, 2235; Angew. Chem. Int. Ed. Engl. 1994, 33, 1089.
21. S. J. Cristol, W. P. Norris, J. Am. Chem. Soc. 1953, 75, 2645.
22. G. Zweifel, C. C. Whitney, J. Am. Chem. Soc. 1967, 89, 2753.
23. 4, 21.4 equiv 10, DMF, 110°C, 60h.
24. 4, 1.7 equiv 11, DMF, 80°C, 60h.
25. 4, 1.5 equiv 2d, DMF, 120°C, 63h.
26. 3CN 1/1, 60°C, 60h.
27. 2O 1/1/0.2, 60°C, 60h.
28. 3), 5.90 (dd, J = 9.8, 6.7 Hz, 1 H, 7-H), 6.03 (d, J = 9.9 Hz, 1 H, 12-H), 6.11 (dd, J = 9.9, 4.5 Hz, 1 H, 11-H), 6.32 (d, J = 9.8 Hz, 1 H, 6-H9, 6.54 (d, J = 2.8 Hz, 1 H, 4-H), 6.68 (dd, J = 8.3, 2.8 Hz, 1 H, 2-H), 7.17 (d, J = 8.3 Hz. 1 H, 1-H).
29. 4, DMF, 60h, 115°C.
30. 2O 1/1/0.2, 4.5h, 115°C.
31. W. A. Herrmann, C. Broßmer, K. Öfele, C.-P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int. Ed. Engl. 1995, 34, 1844.
32. W. A. Herrmann, C. Broßmer, K. Öfele, C.-P. Reisinger, T. Priermeier, M. Beller, H. Fischer, Angew. Chem. 1995, 107, 1989; Angew. Chem. Int. Ed. Engl. 1995, 34, 1844.
33. a) L. F. Tietze, Chem. Rev. 1996, 115;
34. b) L. F. Tietze, U. Beifuß, Angew. Chem. 1993, 105, 137; Angew. Chem. Int. Ed. Engl. 1993, 32, 131.
35. b) L. F. Tietze, U. Beifuß, Angew. Chem. 1993, 105, 137; Angew. Chem. Int. Ed. Engl. 1993, 32, 131.
36. 2O 1/1/0.2, 168h, 60°C, 3/2b 1/1; 35% yield not optimized; 30% 3 could be recovered.
37. 2, 18h, room temperature.