Development and application of bis-hydroxamic acid (BHA)-molybdenum complexes to perform catalytic asymmetric oxidation of olefins and sulfides

ORGN 374

Hisashi Yamamoto, yamamoto@uchicago.edu and Allan Barlan, abarlan@uchicago.edu. Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637
A new chiral Bis-Hydroxamic Acid (BHA)-Molybdenum complex performs catalytic asymmetric oxidation of olefins and sulfides. The use of achiral oxidants with molybdenum catalyst in air at room temperature can tolerate a range of terminal, cis-, and tri-substituted olefins that can provide good to excellent selectivity and yields. Furthermore, this approach oxidizes the most electron rich alkene in the presence of multiple double bonds, by the direct oxidation of myrcene and squalene. In addition to oxidation of olefins, this method utilizes one equivalent of alkyl peroxide to oxidize sulfides in air with yields up to 83% and ee up to 86%. An extension of our methodology combines the asymmetric oxidation with kinetic resolution providing excellent enantioselectivity (ee 92-99%).
 

Asymmetric Reactions and Syntheses
1:00 PM-5:00 PM, Tuesday, March 27, 2007 McCormick Place East -- Room E351, Level 3, Oral

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007