Copper-catalyzed enantioselective decarboxylative cyanation of β,γ-unsaturated carboxylic acids to access chiral allyl nitriles

Abstract

Copper-catalyzed asymmetric radical cyanation reactions have emerged as a powerful platform for construction of a variety of enantioenriched cyano-containing compounds under mild conditions. Herein, we report a copper-catalyzed enantioselective decarboxylative cyanation of readily available β, γ -unsaturated carboxylic acids promoted by a hypervalent iodine(III) reagent. The key allyl radical can be efficiently formed through single-electron reduction of in-situ -generated phenyliodine(III) dicarboxylates by Cu(I) species. This protocol features mild conditions, wide substrate scope, and functional group tolerance, producing a diverse range of chiral allyl nitriles in moderate to good yields and with high regio- and enantioselectivities. The enantioenriched allyl nitrile products can be used for the preparation of various synthetically useful chiral intermediates through simple transformations. • Copper-catalyzed asymmetric radical cyanation reactions are developed • Enantioselective decarboxylative cyanation of β,γ -unsaturated carboxylic acids is shown • The reaction is promoted by a hypervalent iodine(III) reagent • Efficient generation of the highly reactive allyl radical powers the reaction Copper-catalyzed asymmetric radical cyanation reactions have emerged as a powerful platform for construction of enantioenriched cyano-containing compounds under mild conditions. Zhang and Huang et al. develop a copper-catalyzed enantioselective decarboxylative cyanation of readily available β,γ-unsaturated carboxylic acids promoted by a hypervalent iodine(III) reagent.