Silylene Transfer to Carbonyl Compounds and Subsequent Ireland−Claisen Rearrangements to Control Formation of Quaternary Carbon Stereocenters
datasetposted on 2005-02-23, 00:00 authored by Stacie A. Calad, K. A. Woerpel
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 α,β-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.
Silylene transferestersQuaternary Carbon StereocentersSubsequentcommunicationIrelandControl FormationCarbonyl Compoundsstereoselective enolate formationsilylene transfercyclic silyl ketene acetal functionalityintermediatemethodaldol addition reactionsstereocenterregioRearrangementcarbonyl compoundsSilylene Transferquaternary carbon centersoxasilacyclopentenerearrangement