Asymmetric Allylic Alkylation of Ketone Enolates: An Asymmetric Claisen Surrogate

Abstract
The combination of catalytic palladium(0) and Trost ligand provides an effective catalyst for the rearrangement of allyl β-ketoesters. The mechanism of the transformation involves formation of π-allyl palladium intermediates which undergo enantioselective attack by ketone enolates. Decarboxylation of β-ketocarboxylates allows regiospecific generation of enolates under extremely mild conditions.