Photocatalytic Synthesis of <i>α</i> ‐Trifluoromethyl Amidines and <i>α</i> ‐Trifluoromethyl Imidates from Isocyanides and Trifluoroacetylsilanes ^†

Comprehensive Summary α‐ Trifluoromethyl amidines and imidates represent privileged molecular scaffolds due to the prevalence of amidine/imidate motifs in bioactive compounds and functional materials, coupled with the ability of the CF 3 group to enhance key physicochemical and pharmacological properties. Nevertheless, general methods for their synthesis remain underdeveloped. Herein, we report a mild, metal‐ free photocatalytic strategy that enables the modular assembly of these valuable structures with perfect atom economy. The protocol involves the in situ generation of 3‐(trifluoromethyl)ketenimines from readily accessible trifluoroacylsilanes and isocyanides, followed by nucleophilic trapping with anilines and phenols. This operationally simple method exhibits a broad substrate scope, high efficiency, and generally delivers products in good yields. Mechanistic investigations, supported by density functional theory (DFT) calculations, indicate that the reaction proceeds preferentially via a triplet carbene intermediate, and a plausible mechanism for the pivotal coupling step is proposed.