Dialkylation of Vinyl Arenes under Cobalt Catalysis

Herein, a directing group and ligand-free cobalt-catalyzed alkene dialkylation with various alkyl halides and alkylzinc pivalates is reported. This method is distinguished by its broad scope, synthetic simplicity, and excellent regio- and chemoselectivities, thus providing a modular platform for the rapid synthesis of C(sp3)-rich carbogenic skeletons via 2-fold C(sp3)–C(sp3)/C(sp3)–C(sp3) bond formation. Moreover, the controllable transformations with those polyhaloalkanes, such as simple C1 synthons of CF2Br2, CCl4, or CBr4, as well as their derivatives are of special interest, which should find potential applications in both synthetic and medicinal chemistry.