Electron Donor–Acceptor Complex-Driven Minisci Reactions of N-Heteroaromatic and Inert C(sp ³ )–H without Brønsted Acids and External Oxidants

We report a direct Minisci-type reaction of N -heteroaromatics via electron donor–acceptor (EDA) complex photochemistry. This method employs sulfonium salts as versatile electron acceptors to facilitate Minisci Reactions with unactivated C(sp 3 )–H bonds (ethers, alkanes, amides) and N–H (amides), P–H (phosphites), and Si–H partners, eliminating the need for prefunctionalized radical precursors, photocatalysts, stoichiometric external oxidants, and Brønsted acids. The aryl radical generated in situ acts as a hydrogen-atom transfer (HAT) agent, abstracting a hydrogen atom from the inert substrate to generate nucleophilic radicals that couple with the N-heteroaromatic. This approach demonstrates broad substrate scope, accommodating diverse N-heteroaromatics (phenanthridines, isoquinolines, quinolines, acridines, benzothiazoles, etc., including acid-sensitive and bioactive molecules such as N-acetyl fasudil) and various inert partners, achieving good to excellent yields.