Rhodium-catalyzed asymmetric allylic substitution with hard nucleophiles

ORGN 255

Frederic Menard, fmenard@chem.utoronto.ca, Christopher J. Dockendroff, Timothy M. Chapman, and Mark Lautens, mlautens@chem.utoronto.ca. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada
A highly enantioselective rhodium(I)-catalyzed desymmetrization of a meso-cyclic allylic dicarbonate with organoboronic acid nucleophiles is reported. The rhodium(I) catalyst formed in situ from [Rh(cod)OH]2, and Xyl-P-PHOS allowed the SN2' allylic substitution product to be obtained with a range of arylboronic acids in enantiomeric excesses of up to 92% with regioselectivities of up to >20:1. This reaction allows access to high added value compounds.

 

Asymmetric Reactions and Syntheses
8:00 AM-11:40 AM, 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