Theoretical mechanistic study of nickel-catalyzed anti-Markovnikov hydroarylation of alkenes

Transition metal-catalyzed hydroarylation of alkenes can provide various Markovnikov products, but so-called anti-Markovnikov additions to alkenes are rarely reported. Here, a divalent nickel hydride complex catalyzed anti-Markovnikov reductive cross-coupling of styrene and aryl iodide has been investigated using density functional theory. The reaction occurs via the regio-determining hydronickelation, the oxidative addition of the C-I bond to Ni(II) center, and the rate-determining reductive elimination of hydroarylation product. The electronic processes were investigated with a fragment molecular orbital analysis to understand the origin of anti-Markovnikov selectivity and successive oxidative addition and reductive elimination steps.