Palladium-Catalyzed Regiospecific Decarboxylative Allylation of (Cyclohexadienylidene)malononitriles: Access to α-Allyl-α-aryl Malononitriles.

ABSTRACT

A palladium-catalyzed regiospecific decarboxylative ε-allylation of (cyclohexadienylidene)malononitriles is presented for the synthesis of functionalized α-allyl-α-aryl malononitriles. This reaction proceeds via a resonance-stabilized α-aryl malononitrile anion, resulting in a wide range of α-allyl-α-aryl malononitriles in high yields with excellent linear product selectivity. We have also shown that the resulting products can be transformed into valuable synthetic intermediates by decyanation and Mizoroki-Heck arylation. In addition, an enantioselective decarboxylative allylation reaction is also presented.