A General Platform for Aryl/Alkyl Radical Functionalization Enabled by Photoinduced Electron Donor–Acceptor Complex

Organic bromo- and boryl groups have long been recognized as essential building blocks in the synthesis of functionalized aromatics and alkanes. Dibenzothiophenium salts have recently emerged as powerful alternatives to conventional organic bromine- and boron-based building blocks, demonstrating excellent selectivity independent of electronic effects or steric constraints. Herein, we describe a simple photoinduced EDA complex based on sulfonium salts and Hantzsch ester, enabling site-selective functionalization of readily available arenes under mild and uniform reaction conditions via phenylsulfonyl-based SOMO-philes. In addition, we also utilized this general platform to achieve challenging conversion of alkyl alcohols. This simple metal-free protocol facilitates diverse aryl/alkyl functionalizations at room temperature, such as sulfurization, disulfurization, selenation, fluoroalkylthiolation, allylation, alkenylation, and alkynylation. This strategy offers excellent functional group compatibility and enables the site-selective functionalization of complex, multisubstituted bioactive molecules and druglike scaffolds.