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Density Functional Theory Study on Mechanism and Selectivity of Nickel-Catalyzed Hydroboration of Vinylarenes

Jingwei Wu, Yongzhu Zhou, Lei Zhang, Jie Zhang, Pei Song, Xiaoling Wang, Cuihong Wang

Organics · pp. 30–30 · Published 11 Jul 2025

10.3390/org6030030

Abstract

Density functional theory calculations were performed to elucidate the mechanistic details and origins of the selectivity of the nickel-catalyzed hydroboration of vinylarenes using B2pin2/MeOH. The catalytic cycles involved four sequential elementary steps: hydronickelation, anion exchange, transmetalation, and reductive elimination. Kinetic analyses identified hydronickelation as the rate-determining step with an activation barrier of 19.8 kcal/mol, while transmetalation proceeded through a stepwise mechanism characterized by two distinct transition states. Comprehensive analyses of the relevant transition structures and energetics demonstrated that the observed R-enantioselectivity (94% ee) originated from favorable nonbonding interactions. Lastly, our calculations suggested that the Markovnikov regioselectivity was predominantly governed by steric factors rather than electronic effects.

Hydroboration Selectivity Nickel Chemistry Catalysis Density functional theory Mechanism (biology) Computational chemistry

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