Theoretical Rationale for Regioselection in Phosphine-Catalyzed Allenoate Additions to Acrylates, Imines, and Aldehydes

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Org. Lett., 8 (17), 3643 -3646, 2006. 10.1021/ol061095y S1523-7060(06)01095-9
Web Release Date: July 20, 2006

Theoretical Rationale for Regioselection in Phosphine-Catalyzed Allenoate Additions to Acrylates, Imines, and Aldehydes

Travis Dudding,* Ohyun Kwon, and Evan Mercier

Department of Chemistry, Brock University, St. Catharines, Ontario LS2 3A1, Canada, and Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569

tdudding@brocku.ca

Received May 4, 2006

Abstract:

A rationale for regioselection in phosphine-promoted annulations of acrylates, imines, and aldehydes with allenoates has been developed using computation at the B3LYP/6-31G(d) level of theory. The computed transition states revealed that Lewis acid activation, strong hydrogen bonding (H-bonding), and minimization of unfavorable van der Waals contacts are the guiding factors responsible for regioselection. An excellent level of correlation between the calculated regioselectivities and experiment was observed.

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