Photocatalytic Synthesis of α-Trifluoromethyl Amidines and α-Trifluoromethyl Imidates from Isocyanides and Trifluoroacetylsilanes
Yuan Yao , Gang Zhou , Shanshan Liu , Xiaotian Qi , Xiaoqian He , Xiao Shen
Chinese Journal of Chemistry ›› 2026, Vol. 44 ›› Issue (10) : 1624 -1630.
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 CF3 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.
3-(Trifluoromethyl)ketenimines / α-Trifluoromethy amidines / α-Trifluoromethy imidates / Trifluoroacetylsilanes / Triplet carbene
2026 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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