Transition metal-catalyzed [5 + 2] cycloadditions of 2-substituted-1-vinylcyclopropanes: Catalyst control and reversal of regioselectivity

Organic Letters

Volumn 1, Issue 13, 1999, Pages 2089-2092

  Wender, Paul A ^a   Dyckman, Alaric J ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001758137     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol991171f     Document Type: Article

References (14)

1. Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720-4721.
2. Wender, P. A.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1998, 120, 1940-1941. Wender, P. A.; Husfeld, C. O.; Langkopf, E.; Love, J. A.; Pleuss, N. Tetrahedron 1998, 54, 7203-7220.
3. Wender, P. A.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1998, 120, 1940-1941. Wender, P. A.; Husfeld, C. O.; Langkopf, E.; Love, J. A.; Pleuss, N. Tetrahedron 1998, 54, 7203-7220.
4. Wender, P. A.; Glorius, F.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1999, 121, 5348-5349.
5. Wender, P. A.; Sperandio, D. J. Org. Chem. 1998, 63, 4164-4165.
6. (a) Wender, P. A.; Rieck, H.; Fuji, M. J. Am. Chem. Soc. 1998, 120, 10976-10977.
7. (b) For an isolated example of an intermolecular [5 + 2] cycloaddition, see: Binger, P.; Wedmann, P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113-119.
8. For other work related to metal-catalyzed [5 + 2] cycloadditions, see: Gilbertson, S. R.; Hoge, G. S. Tetrahedron Lett. 1998, 39, 2075-2078.
9. For selectivity in vinylcyclopropane bond cleavage, see: Ryu, I.; Ikura, K.; Tamura, Y.; Maenaka, J.; Ogawa, A.; Sonoda, N. Synlett 1994, 941-942. Hayashi, M.; Ohmsato, T.; Meng, Y.-P.; Saigo, K. Angew. Chem., Int. Ed. 1998, 837-840.
10. For selectivity in vinylcyclopropane bond cleavage, see: Ryu, I.; Ikura, K.; Tamura, Y.; Maenaka, J.; Ogawa, A.; Sonoda, N. Synlett 1994, 941-942. Hayashi, M.; Ohmsato, T.; Meng, Y.-P.; Saigo, K. Angew. Chem., Int. Ed. 1998, 837-840.
11. (a) Wender, P. A.; Dyckman, A. J.; Husfeld, C. O.; Kadereit, D.; Love, J. A. Rieck, H. J. Am. Chem. Soc. 1999, 121, 10442-10443.
12. (b) The reactions of 3, 7, and 17 with modified Wilkinson's catalyst were previously reported in ref 8a. They are included here for ease of comparison.
13. A racemic mixture was used in all cases. Only one enantiomer is depicted for simplicity.
14. For brevity, only one mechanistic possibility is presented. An alternative set of mechanistic possibilities can be formulated around the initial formation of metallacyclohexenes followed by coordination to the tethered alkyne and convergence on the advanced intermediates E and E′ (see ref 5a). While differing in the timing of connections, the issues of regio-and stereoselectivty are treated similarly.