Palladium-Catalyzed para-Selective Allylation of 1-(Cyanomethyl)arenes with Allyl Acetates

Abstract

The Pd/PMe 3 -catalyzed allylation of 1-(cyanomethyl)naphthalenes with allyl acetates proved to be para-rather than αregioselective. This reaction is thought to proceed through ligand attack of the para-carbon in the arenes, electronically enriched by a cyano-stabilized α-carbanion, to the (π-allyl)palladium and a 1,5-hydrogen shift of the parahydrogen from the dearomatized intermediate.