Cyclopalladated ferrocenyl amines as enantioselective catalysts for the rearrangement of allylic imidates to allylic amides

Tetrahedron Letters

Volumn 38, Issue 51, 1997, Pages 8837-8840

  Hollis, T Keith ^a   Overman, Larry E ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; AMIDE;

ARTICLE; CATALYSIS; CHIRALITY; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030783848     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10385-9     Document Type: Article

References (23)

1. (a) Overman, L. E. J. Am. Chem. Soc. 1974, 96, 597.
2. (b) Overman, L. E. J. Am. Chem. Soc. 1976, 98, 2901.
3. (c) Overman, L. E. Acc. Chem. Res. 1980, 13, 218.
4. Representative examples are cited in reference 3.
5. Calter, M.; Hollis, T. K.; Overman, L. E.; Ziller, J.; Zipp, G. G. J. Org. Chem. 1997, 62, 1449.
6. (a) Cope, A. C.; Friedrich, E. C. J. Am. Chem. Soc. 1968, 90, 909.
7. (b) For a recent review with leading references see: Canty, A. J. in Comprehensive Organometallic Chemistry II 1995, 9, 242-248.
8. We speculate that coordination of the imidate nitrogen with the cationic metal center promotes the competing ionization reaction observed with catalysts such as 1.
9. Cross, R. J. Adv. Inorg. Chem. 1989, 34, 219.
10. Purchased from Aldrich Chemical Company.
11. Kuzmina, L. G.; Struchkov, Y. T.; Troitskaya, L. L.; Jokolov, V. I.; Reumov, O. A. Izv. Akad. Nauk. SSSR, Ser. Khim. 1979, 1528.
12. This complex forms with complete diastereoselectivity at nitrogen.
13. (a) Sokolov, V. I.; Troitskaya, L. L.; Reutov, J. J. Organomet. Chem. 1977, 133, C28.
14. (b) Sokolov, V. I.; Troitskaya, L. L.; Reutov, J. Dokl. Akad. Nauk SSSR 1977, 236, 371.
15. (c) Lopez, C.; Bosque, R.; Solans, X.; Font-Bardia, M. Tetrahedron: Asymm. 1996, 7, 2527.
16. 11
17. Details of single crystal X-ray structures for 6a, 6f and the acac complex derived from 7a will be reported elsewhere.
18. 11 and found to be poor catalysts for the rearrangement of 2, producing 3 in 15% yield (59% ee) after 10 d and 55% yield (20% ee) after 2 d, respectively.
19. Hockless, D. C. R.; Gugger, P. A.; Leung, P.-H.; Mayadunne, R. C.; Pabel, M.; Wild, S. B. Tetrahedron 1997, 53, 4083.
20. 2 (0.5 mL) were combined and left to stand for 24 h. The solution was concentrated and the residue was chromatographed on silica gel (4% EtOAc-hexanes) yielding 3-(N-Phenyl)-1-hexenylbenzamide (3, 14.3 mg, 97%). Enantiopurity was determined by HPLC analysis using a Chiracel AS column (96:4 hexanes-i-propanol).
21. Imidates were prepared by standard procedures; see reference 3 for leading references.
22. 2 as catalyst.
23. Overman, L. E.; Zipp, G. G. J. Org. Chem. 1997, 62, 2288.