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

A palladium-catalyzed regiospecific decarboxylative epsilon-allylation of (cyclohexadienylidene)malononitriles is presented for the synthesis of functionalized alpha-allyl-alpha-aryl malononitriles. This reaction proceeds via a resonance-stabilized alpha-aryl malononitrile anion, resulting in a wide range of alpha-allyl-alpha-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.

Automated summary

A palladium-catalyzed regiospecific decarboxylative epsilon-allylation of (cyclohexadienylidene)malononitriles was developed for the synthesis of functionalized alpha-allyl-alpha-aryl malononitriles, resulting in a wide range of products with high yields and excellent linear selectivity. The resulting products can be further transformed into valuable synthetic intermediates through decyanation and Mizoroki-Heck arylation. Additionally, an enantioselective decarboxylative allylation reaction was also demonstrated in the study.