Stereoselective umpolung aldehyde reactions using chiral nucleophilic carbenes as catalysts

ORGN 296

Tomislav Rovis, rovis@lamar.colostate.edu, Department of Chemistry, Colorado State University, Fort Collins, CO 80523
Polarity reversal approaches (umpolung) provide new ways to think about bond disconnections. We have developed a family of catalysts capable of effecting the umpolung addition of aldehydes into Michael acceptors (the Stetter reaction) with high stereoselectivity. The process tolerates substitution at both alpha and beta positions on the Michael acceptor and is capable of forming quaternary as well as contiguous stereocenters. The application to dienone acceptors allows for control of up to three contiguous stereocenters with excellent enantioselectivity. We have further identified new reactivity associated with these catalysts. The development of these reactions and their application to total synthesis will be discussed.
 

Organocatalysis
1:00 PM-5:05 PM, Monday, 11 September 2006 Moscone Center -- Room 135, Oral

Division of Organic Chemistry

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