Nickel‐Catalyzed Regioselective Intermolecular Dialkylation of Alkenylarenes: Generation of Two Vicinal C(sp3)−C(sp3) Bonds Across Alkenes**.

We disclose a Ni‐catalyzed regioselective dialkylation reaction of alkenylarenes with α‐halocarbonyls and alkylzinc reagents. The reaction produces γ‐arylated alkanecarbonyl compounds with the generation of two new C(sp3)−C(sp3) bonds at the vicinal carbons of alkenes. This reaction is effective for the use of primary, secondary and tertiary α‐halocarboxylic esters, amides and ketones in conjunction with primary and secondary alkylzinc reagents as the sources of two C(sp3) carbons for the dialkylation of terminal and cyclic internal alkenes. [ABSTRACT FROM AUTHOR]