Photochemical Trifluoromethylative Difunctionalization of Styrenes and Phenylacetylenes via a Catalytic EDA Platform

Abstract Herein we report a visible‐light‐induced trifluoromethylative difunctionalization of styrenes and phenylacetylenes using trifluoromethyl thianthrenium triflate (TT‐CF 3 + OTf − ). The transformation was enabled by the discovery of a photoactive catalytic EDA complex formed between carbazolyl dithiocarbamate and TT‐CF 3 + OTf − . This three‐component reactivity platform establishes a new paradigm for TT‐CF 3 + OTf − , significantly expanding its repertoire of photochemically enabled trifluoromethylation reactions.