A General Hydrotrifluoromethylation of Unactivated Olefins Enabled by Voltage-Gated Electrosynthesis.

ABSTRACT: Here we present the first successful hydrotrifluoromethylation of unactivated olefins under electrochemical conditions. Commercially available trifluoromethyl thianthrenium salt (TT⁺-CF₃BF₄ ^-, E_p/2=-0.85 V vs Fc/Fc⁺) undergoes electrochemical reduction to generate CF₃ radicals which add to olefins with exclusive chemoselectivity. The resulting carbon centered radical undergoes a second cathodic reduction, instead of a classical HAT process, to generate a carbanion that can be terminated by protonation from solvent. The use of MgBr₂ (+0.20 V onset oxidation potential) plays a key role as an enabling sacrificial reductant for the reaction to operate in an undivided cell. Guided by cyclic voltammetry (CV)

SUBMITTER: Alvarez EM 

PROVIDER: S-EPMC11753607 | biostudies-literature | 2025 Jan

REPOSITORIES: biostudies-literature