Silver-Catalyzed 1,3-Ditrifluoromethoxylation and 1,3-Fluorotrifluoromethoxylation of Arylcyclopropanes

Despite the existence of two synthetic methods for installing dual OCF₃ groups, both are limited to 1,2-selectivity, and the strategic incorporation of bis(trifluoromethoxy) groups at 1,3-positions remains unexplored. Herein, we developed the first silver-catalyzed 1,3-ditrifluoromethoxylation of arylcyclopropanes, which provides efficient access to a series of synthetically valuable 1,3-bis(trifluoromethoxy)-substituted architectures. Additionally, the reaction also allows for the simultaneous incorporation of both fluorine and trifluoromethoxy groups at the 1,3-positions in electron-rich arenes by fine-tuning the reaction conditions. This method demonstrates broad substrate scope, excellent functional group tolerance, and applicability to late-stage modification of complex molecules.