Electrochemical aminotrideuteromethylthiolation of isocyanides with anilines and CD3SSO3Na†

Herein, we describe an electrochemical strategy that enables the aminotrideuteromethylthiolation of isocyanides with anilines and CD₃SSO₃Na, providing an unprecedented route to access S-CD₃ isothioureas in satisfactory yields. Mechanistic studies reveal that the transformation is initiated via the addition of the CD₃S radical to the isocyanide, followed by a nucleophilic attack on the in situ generated imine carbocation intermediate by anilines. Importantly, these reactions exhibit exclusive chemoselectivity at the carbon of isocyanides and wide functional group compatibility as well as enable late-stage functionalization of complex substrates.