The Silicon–Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes
Hui Zhou, Han Yong Bae, Markus Leutzsch, Jennifer L. Kennemur, Diane Bécart, Benjamin List
Abstract
chiral reagents. We now describe a catalytic approach in which strongly acidic and confined imidodiphosphorimidates (IDPi) catalyze highly enantioselective interconversions of ketones and enol silanes. These "silicon-hydrogen exchange reactions" enable access to enantiopure enol silanes via tautomerizing σ-bond metatheses, either in a deprotosilylative desymmetrization of ketones with allyl silanes as the silicon source or in a protodesilylative kinetic resolution of racemic enol silanes with a carboxylic acid as the silyl acceptor.
Topics & Concepts
SilanesEnantiopure drugChemistryEnolEnantioselective synthesisSilylationOrganic chemistryMetathesisCatalysisCombinatorial chemistrySilanePolymerPolymerizationSynthetic Organic Chemistry MethodsOrganoboron and organosilicon chemistryAsymmetric Hydrogenation and Catalysis