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 <i>N</i>-heteroaromatics via electron donor-acceptor (EDA) complex photochemistry. This method employs sulfonium salts as versatile electron acceptors to facilitate Minisci Reactions with unactivated C(sp³)-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.