J. Am. Chem. Soc., 126 (30), 9154 -9155, 2004. 10.1021/ja048739m S0002-7863(04)08739-6
Web Release Date: July 3, 2004

Copyright © 2004 American Chemical Society

On the Mechanism of [Rh(CO)2Cl]2-Catalyzed Intermolecular (5 + 2) Reactions between Vinylcyclopropanes and Alkynes

Zhi-Xiang Yu, Paul A. Wender,* and K. N. Houk*

Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, and Department of Chemistry, Stanford University, Stanford, California 94305

houk@chem.ucla.edu; wenderp@stanford.edu

Received March 4, 2004

Abstract:

DFT calculations have been applied to investigate the reaction mechanism of rhodium dimer, [Rh(CO)2Cl]2, catalyzed intermolecular (5 + 2) reactions between vinylcyclopropanes and alkynes. The catalytic species is Rh(CO)Cl and the catalytic cycle is through the sequential reactions of cyclopropyl cleavage of vinylcyclopropane, alkyne insertion (rate-determining step), and a migratory reductive elimination.

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