Stereoselective synthesis of an immunomodulator (+)-conagenin using dirhodium(II)-catalyzed C-H amination and chelation-controlled reductions as key steps

Synlett

Volumn , Issue 6, 2006, Pages 930-932

  Yakura, Takayuki ^a   Yoshimoto, Yuya ^a   Ishida, Chisaki ^a   Mabuchi, Shunsuke ^a  

^a UNIVERSITY OF TOYAMA   (Japan)

Author keywords

C H amination; Chelation control; Conagenin; Dirhodium(II); Immunomodulator; Reduction

Indexed keywords

CONAGENIN; IMMUNOMODULATING AGENT; METHYL 3 HYDROXY 2 METHYLPROPANOATE; PROPIONIC ACID DERIVATIVE; RHODIUM DERIVATIVE; UNCLASSIFIED DRUG;

AMINATION; ARTICLE; CATALYSIS; CHELATION; DRUG STRUCTURE; DRUG SYNTHESIS; STEREOCHEMISTRY;

EID: 33645762785     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-933145     Document Type: Article

References (31)

1. Yamashita, T.; Iijima, M.; Nakamura, H.; Isshiki K.; Naganawa, H.; Hattori, S.; Hamada, M.; Ishizuka, M.; Takeuchi, T.; Iitaka, Y. J. Antibiot. 1991, 44, 557.
2. (a) Kawatsu, M.; Yamashita, T.; Osono, M.; Ishizuka, M.; Takeuchi, T. J. Antibiot. 1993, 46, 1687.
3. (b) Kawatsu, M.; Yamashita, T.; Ishizuka, M.; Takeuchi, T. J. Antibiot. 1994, 47, 1123.
4. (c) Ishizuka, M.; Kawatsu, M.; Yamashita, T.; Ueno, M.; Takeuchi, T. Int. J. Immunopharmacol. 1995, 17, 133.
5. (a) Kawatsu, M.; Yamashita, T.; Ishizuka, M.; Takeuchi, T. J. Antibiot. 1995, 48, 222.
6. (b) Hamada, M.; Sonotake, E.; Yamamoto, S.; Moriguchi, S. J. Antibiot. 1999, 52, 548.
7. (c) Hamada, M.; Yamamoto, S.; Moriguchi, S.; Kishino, Y. J. Antibiot. 2001, 54, 349.
8. (a) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047.
9. (b) Sano, S.; Miwa, T.; Hayashi, K.; Nozaki, K.; Ozaki, Y.; Nagao, Y. Tetrahedron Lett. 2001, 42, 4029.
10. (c) Matsukawa, Y.; Isobe, M.; Kotsuki, H.; Ichikawa, Y. J. Org. Chem. 2005, 70, 5339.
11. Enders, D.; Bartsch, M.; Runsink, J. Synthesis 1999, 243.
12. (a) Kovács-Kulyassa, Á.; Herczegh, P.; Sztaricskai, F. J. Tetrahedron Lett. 1996, 37, 2499.
13. (b) Kovács-Kulyassa, Á.; Herczegh, P.; Sztaricskai, F. Tetrahedron 1997, 53, 13883.
14. Rodrigues, J. A. R.; Moran, P. J. S.; Milagre, C. D. F.; Ursini, C. V. Tetrahedron Lett. 2004, 45, 3579.
15. (a) Review: Banfi, L.; Guanti, G. Synthesis 1993, 1029.
16. (b) Recent report: Dias, L. C.; Melgar, G. Z.; Jardim, L. S. A. Tetrahedron Lett. 2005, 46, 4427.
17. Espino, C. G.; Du Bois, J. Angew. Chem. Int. Ed. 2001, 40, 598.
18. Review: Davies, H. M. L.; Long, M. S. Angew. Chem. Int. Ed. 2005, 44, 3518.
19. Applications to natural product synthesis: (a) Hinman, A.; Du Bois, J. J. Am. Chem. Soc. 2003, 125, 11510.
20. (b) Parker, K. A.; Chang, W. Org. Lett. 2003, 5, 3891.
21. (c) Parker, K. A.; Chang, W. Org. Lett. 2005, 7, 1785.
22. (d) Bodner, R.; Marcellino, B. K.; Severino, A.; Smenton, A. L.; Rojas, C. M. J. Org. Chem. 2005, 70, 3988.
23. Kocovsky, P. Tetrahedron Lett. 1986, 27, 5521.
24. All other attempts under several conditions [using various dirhodium(II) catalysts, hypervalent iodine reagents, solvents] gave poorer yields of cyclization product. Development of an alternative route using C-H amination has been investigated and will be reported.
25. Ishizuka, T.; Kunieda, T. Tetrahedron Lett. 1987, 28, 4185.
26. Hatakeyama, S.; Matsumoto, H.; Fukuyama, H.; Mukugi, Y.; Irie, H. J. Org. Chem. 1997, 62, 2275.
27. 9
28. Nakano, M.; Kikuchi, W.; Matsuo, J.; Mukaiyama, T. Chem. Lett. 2001, 424.
29. Nakata, T.; Tani, Y.; Hatozaki, M.; Oishi, T. Chem. Pharm. Bull. 1984, 32, 1411.
30. 3)}: Davies, S. G.; Edwards, A. J.; Evans, G. B.; Mortlock, A. A. Tetrahedron 1994, 50, 6621.
31. The stereochemistries of neither diastereomer were determined.