Silylene transfer to carbonyl compounds and subsequent Ireland-Claisen rearrangements to control formation of quaternary carbon stereocenters.
In this communication, we demonstrate that silylene transfer to carbonyl compounds provides a new method for regio- and stereoselective enolate formation. Silylene transfer to a range of alpha,beta-unsaturated esters under silver-catalyzed conditions proved to be a general method for the formation of oxasilacyclopentenes containing a cyclic silyl ketene acetal functionality. These oxasilacyclopentenes are useful synthetic intermediates that can undergo facile and selective Ireland-Claisen rearrangements and aldol addition reactions to provide products with multiple contiguous stereocenters and quaternary carbon centers.
Calad
Stacie A
SA
Department of Chemistry, University of California, Irvine, California 92627-2025, USA.
Woerpel
K A
KA
D000475:Alkenes / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods; D004952:Esters / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D004952:Esters; D012821:Silanes