Ligand‐Enabled Nickel‐Catalyzed Redox‐Relay Migratory Hydroarylation of Alkenes with Arylborons

Abstract A redox‐relay migratory hydroarylation of isomeric mixtures of olefins with arylboronic acids catalyzed by nickel complexes bearing diamine ligands is described. A range of structurally diverse 1,1‐diarylalkanes, including those containing a 1,1‐diarylated quaternary carbon, were obtained in excellent yields and with high regioselectivity. Preliminary experimental evidence supports the proposed non‐dissociated chainwalking of aryl‐nickel(II)‐hydride species along the alkyl chain of alkenes before selective reductive elimination at a benzylic position. A catalyst loading as low as 0.5 mol % proved to be sufficient in large‐scale synthesis while retaining high reactivity, highlighting the practical value of this transformation.