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

Jiandong GuoDongju ZhangXiaotai Wang
Published in: Dalton transactions (Cambridge, England : 2003) (2021)
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[double bond, length as m-dash]C, a carbon radical rebound to nickel to facilitate chemoselective defluorination, and a two-state reactivity of Ni(ii) enabling σ-bond metathesis with PhSiH3 to regenerate the catalyst. The findings can have implications for developing new metal hydride HAT-initiated reactions.
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