Heteroleptic Nickel Complexes for the Markovnikov-Selective Hydroboration of Styrenes

First-row transition metal catalysis offers a cheaper, more environmentally sustainable alternative to second- and third-row transition metal catalysts. Nickel has shown great promise as a tool for the borylation of unsaturated compounds to yield boronic esters, but Markovnikov-selective hydroborations of simple styrenes have not been well-explored. Herein, we report the synthesis of benzyl boronic esters via nickel-catalyzed hydroboration of styrenes using a heteroleptic N-heterocyclic carbene (NHC)–phosphine nickel complex, IMes­(Cy₃P)­NiCl₂. The IMes­(Cy₃P)­NiCl₂ complex displays a broad substrate scope and maintains the integrity of yield and regioselectivity when challenged with substrates bearing increased steric hindrance. The heteroleptic complexes also tolerate both electron-withdrawing and -donating groups, in contrast to traditional bis-phosphine and Ni(0) complexes.