Irradiation of Bifunctional Masked Ketone Pro-Aromatics Unveils Autoinductive Autocatalysis via Electron Donor–Acceptor (EDA) Complexes

We disclose an autocatalytic electron donor–acceptor (EDA) strategy by reutilizing redox auxiliary byproducts as in situ acceptors, enabling an external initiator-free activation of pro-aromatic dihydroquinazolinones (DHQZs). Spectroscopic and DFT data support the Lewis acid-enhanced aggregate formation where DHQZ serves as both donor and latent acceptor through its quinazolinone byproduct. Kinetic studies reveal a kinetic profile specifically representing autoinductive autocatalysis. This platform enables Giese-type acylation/alkylation, desulfonylation, and Minisci reactions, forging C–C, C–N, C–S, and C–Se bonds under mild conditions.