Addition of azaenolates to simple, unactivated olefins

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 22, 1997, Pages 2491-2493

  Kubota, Katsumi ^a   Nakamura, Eiichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

Alkenes; Hydrazones; Ketones; Zinc

Indexed keywords

EID: 0031469196     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199724911     Document Type: Article

References (17)

1. A. T. Nielsen, W. J. Houlihan, Org. React. 1968, 16, 1-438; T. Mukaiyama, ibid. 1982, 28, 203-331.
2. A. T. Nielsen, W. J. Houlihan, Org. React. 1968, 16, 1-438; T. Mukaiyama, ibid. 1982, 28, 203-331.
3. -1, as calculated for free acetone enolate + ethylene, HF/3-21 + G).
4. To improve the unfavorable thermodynamics a) the ring strain of a cyclic olefin was used (E. Nakamura, K. Kubota, J. Org. Chem. 1997, 62, 792-793)
5. B cation (P. Karoyan, G. Chassaing, Tetrahedron Lett. 1997, 38, 85-88; E. Lorthiois, I. Marek, J. F. Normant, ibid. 1997, 38, 89-92).
6. B cation (P. Karoyan, G. Chassaing, Tetrahedron Lett. 1997, 38, 85-88; E. Lorthiois, I. Marek, J. F. Normant, ibid. 1997, 38, 89-92).
7. Another recent (formally related) solution to the problem is the use of vinylmagnesium bromide as an "activated form" of ethylene (E. Nakamura, K. Kubota, G. Sakata, J. Am. Chem. Soc. 1997, 119, 5457-5458). This reaction, which takes place by a metalla-Claisen rearrangement, may be mechanistically unrelated to the present reaction.
8. Utility of metalated hydrazones in the synthesis of carbonyl compounds is well documented: a) G. Stork, J. Benaim, J. Am. Chem. Soc. 1971, 93, 5938-5939;
9. b) E. J. Corey, D. Enders, Chem. Ber. 1978, 111, 1337-1361 and 1978, 111, 1362-1383;
10. b) E. J. Corey, D. Enders, Chem. Ber. 1978, 111, 1337-1361 and 1978, 111, 1362-1383;
11. c) D. E. Bergbreiter, M. Momongan, Comprehensive Organic Synthesis, Vol. 2 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, pp. 503-526;
12. d) E. J. Corey, S. Knapp, Tetrahedron Lett. 1976, 41, 3667-3668.
13. The structure of the zinc hydrazone is presently unknown. For the structures of lithium hydrazones, see D. B. Collum, D. Kahne, S. A. Gut, R. T. DePue, F. Mohamadi, R. A. Wanat, J. Clardy, G. V. Duyne, J. Am. Chem. Soc. 1984, 106, 4865-4869; R. A. Wanat, D. B. Collum, ibid. 1985, 107, 2078-2082; D. Enders, G. Bachstädter, K. A. M. Kremer, M. Marsch, K. Harms, G. Boche, Angew. Chem. 1988, 100, 1580-1581; Angew. Chem. Int. Ed. Engl. 1988, 27, 1522-1524.
14. The structure of the zinc hydrazone is presently unknown. For the structures of lithium hydrazones, see D. B. Collum, D. Kahne, S. A. Gut, R. T. DePue, F. Mohamadi, R. A. Wanat, J. Clardy, G. V. Duyne, J. Am. Chem. Soc. 1984, 106, 4865-4869; R. A. Wanat, D. B. Collum, ibid. 1985, 107, 2078-2082; D. Enders, G. Bachstädter, K. A. M. Kremer, M. Marsch, K. Harms, G. Boche, Angew. Chem. 1988, 100, 1580-1581; Angew. Chem. Int. Ed. Engl. 1988, 27, 1522-1524.
15. The structure of the zinc hydrazone is presently unknown. For the structures of lithium hydrazones, see D. B. Collum, D. Kahne, S. A. Gut, R. T. DePue, F. Mohamadi, R. A. Wanat, J. Clardy, G. V. Duyne, J. Am. Chem. Soc. 1984, 106, 4865-4869; R. A. Wanat, D. B. Collum, ibid. 1985, 107, 2078-2082; D. Enders, G. Bachstädter, K. A. M. Kremer, M. Marsch, K. Harms, G. Boche, Angew. Chem. 1988, 100, 1580-1581; Angew. Chem. Int. Ed. Engl. 1988, 27, 1522-1524.
16. The structure of the zinc hydrazone is presently unknown. For the structures of lithium hydrazones, see D. B. Collum, D. Kahne, S. A. Gut, R. T. DePue, F. Mohamadi, R. A. Wanat, J. Clardy, G. V. Duyne, J. Am. Chem. Soc. 1984, 106, 4865-4869; R. A. Wanat, D. B. Collum, ibid. 1985, 107, 2078-2082; D. Enders, G. Bachstädter, K. A. M. Kremer, M. Marsch, K. Harms, G. Boche, Angew. Chem. 1988, 100, 1580-1581; Angew. Chem. Int. Ed. Engl. 1988, 27, 1522-1524.
17. For a review of the related chemistry of homoenolates, see I. Kuwajima, E. Nakamura, Comprehensive Organic Synthesis Vol. 2 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, pp. 441-454.