Mechanistic insights into Ni-catalyzed hydrogen atom transfer (HAT)-triggered hydrodefluorination of CF3-substituted atkenes

We report the first computational study on a nickel hydride HAT-initiated catalytic reaction, a novel hydrodefluorination of CF3-substituted aryl alkenes to afford gem-difluoroalkenes. This study provides detailed mechanistic insights into the reaction, including HAT from NiH to C=C, a carbon radical rebound to nickel to facilitate chemoselective defluorination, and a two-state reactivity of Ni (II) enabling sigma-bond metathesis with PhSiH3 to regenerate the catalyst. The findings can have implications for developing new metal hydride HAT-initiated reactions.

Automated summary

This study presents a novel hydrodefluorination reaction initiated by nickel hydride HAT, providing mechanistic insights and implications for developing new metal hydride HAT-initiated reactions.