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

The Pd/PMe3-catalyzed allylation of 1-(cyanomethyl)naphthalenes with allyl acetates proved to be para- rather than aregioselective. This reaction is thought to proceed through ligand attack of the para-carbon in the arenes, electronically enriched by a cyano-stabilized a-carbanion, to the (p-allyl)palladium and a 1,5-hydrogen shift of the parahydrogen from the dearomatized intermediate.

Automated summary

The Pd/PMe3-catalyzed allylation reaction of 1-(cyanomethyl)naphthalenes with allyl acetates showed para-selectivity instead of aregioselectivity. This reaction proceeds through ligand attack on the para-carbon of the arenes, which is electronically enriched by a cyano-stabilized α-carbanion. This leads to the formation of (p-allyl)palladium intermediate and a 1,5-hydrogen shift of the parahydrogen.