Vinyldiazolactones: Novel vinylcarbene precursors of excellent stability and synthetic utility

ORGN 304

Darren Bykowski, dbykowsk@mail.umd.edu, Kou-Hui Wu, and Michael P. Doyle. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742
Acyclic vinyldiazoacetates have been used extensively as vinyl carbene precursors in asymmetric cyclopropanation and C-H insertion reactions. We now report the synthesis and application of vinyldiazolactones to these processes. The unique properties of vinyldiazolactones will be described, in particular the ability to access vinyl substitution patterns that have not been achievable with previously reported vinyldiazoacetates. High enantioselectivities (up to 90%) and exceptional diastereoselectivities are obtained for cyclopropanation and intermolecular C-H insertion reactions using dirhodium catalysts having chiral azetidinone ligands.

 

Asymmetric Reactions and Syntheses
1:00 PM-5:00 PM, Monday, 11 September 2006 Moscone Center -- Room 131, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006