Catalytic Dehydrogenative C-H Imidation of Arenes Enabled by Photo-generated Hole Donation to Sulfonimide

In light of the importance of arylamine derivatives in organic materials, pharmaceuticals, and agrochemicals, the development of efficient aromatic C-H amination has long been sought after. Although many attempts have been made to achieve dehydrogenative C-H amination, the low reactivity of simple arenes renders equimolar coupling with amine derivatives a formidable task in synthetic chemistry. Herein, we report equimolar C-H/N-H coupling of arenes and sulfonimides through dehydrogenative aromatic imidation. Thiswas accomplished by means of a ruthenium-based photoredox mediator that employed the arene as the limiting reagent. A wide range of arenes, such as polycyclic aromatic hydrocarbons and heteroarenes, as well as a variety of sulfonimides, were applicable to the reaction. This electrochemistry-based mechanistic study has uncovered that the coupling reaction is initiated by the oxidation of sulfonimides by the ruthenium catalyst.