Mechanism of Ni-Catalyzed Photochemical Halogen Atom-Mediated C(sp³)-H Arylation.

ABSTRACT: Within the context of Ni photoredox catalysis, halogen atom photoelimination from Ni has emerged as a fruitful strategy for enabling hydrogen atom transfer (HAT)-mediated C(sp³)-H functionalization. Despite the numerous synthetic transformations invoking this paradigm, a unified mechanistic hypothesis that is consistent with experimental findings on the catalytic systems and accounts for halogen radical formation and facile C(sp²)-C(sp³) bond formation remains elusive. We employ kinetic analysis, organometallic synthesis, and computational investigations to decipher the mechanism of a prototypical Ni-catalyzed photochemical C(sp³)-H arylation reaction. Our findings revise the previous mechanistic proposals, first by examining the relevance of SET

SUBMITTER: Cusumano AQ 

PROVIDER: S-EPMC11246173 | biostudies-literature | 2024 Jun

REPOSITORIES: biostudies-literature