Nickel-Catalyzed C-CN Bond Activation and Asymmetric Arylcyanation

Significance

The authors present a highly enantioselective C-CN bond activation and intra­molecular arylcyanation using a nickel catalyst and the chiral phosphine ligand TangPhos. Previous studies by Nakao and Hiyama identified this novel mode of reactivity with alkynes and strained alkenes (J. Am. Chem. Soc. 2004, 126, 13904). The present reaction tolerates substituents in the arylnitrile and olefin moieties, however, sterically demanding or electron-deficient alkene substituents require higher catalyst loadings. Using an allylic ether tether in the reaction resulted in catalyst inhibition and no desired product was obtained.