Asymmetric Catalysis of the [5 + 2] Cycloaddition Reaction of Vinylcyclopropanes and -Systems

J. Am. Chem. Soc., 128 (19), 6302 -6303, 2006. 10.1021/ja058590u S0002-7863(05)08590-2
Web Release Date: April 21, 2006

Asymmetric Catalysis of the [5 + 2] Cycloaddition Reaction of Vinylcyclopropanes and -Systems

Paul A. Wender,* Lars O. Haustedt, Jaehong Lim, Jennifer A. Love, Travis J. Williams, and Joo-Yong Yoon

Departments of Chemistry and Molecular Pharmacology, Stanford University, Stanford, California 94305

wenderp@stanford.edu

Received December 19, 2005

Abstract:

As part of our studies of metal-catalyzed [m + n (+...o)] cycloadditions, we have previously reported the rhodium-catalyzed [5 + 2] cycloaddition of vinylcyclopropanes (VCPs) and -systems. These studies have led to Rh(I) complexes that catalyze these reactions in minutes at room temperature or in water without organic solvents. We describe a comparative evaluation of several chiral catalysts for the [5 + 2] reaction, evaluation of a preferred catalyst, [((R)-BINAP)Rh]⁺SbF₆^-, with substrates differing in substitution and tether types-producing enantiomeric excesses 95% for several systems. A predictive model for the selectivity is also presented.

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