Dual-Role Halogen-Bonding-Assisted EDA-SET/HAT Photoreaction System with Phenol Catalyst and Aryl Iodide: Visible-Light-Driven Carbon-Carbon Bond Formation.

Electron donor-acceptor (EDA) complex-mediated single-electron transfer (SET) is a crucial method for generating carbon radicals. Hydrogen atom transfer (HAT) enables the direct generation of alkyl radicals. We report a dual-role EDA-SET/HAT photoreaction system for carbon-carbon bond formation using a phenol catalyst and aryl iodide. This system facilitates addition of alkyl radicals generated from ethers, amide, sulfide, and cycloalkane to arenes. Mechanistic studies revealed that EDA complex formation is mediated by halogen bonding between phenoxide and aryl iodide. Irradiation of the EDA complex with visible light generates an aryl radical, which abstracts a hydrogen atom from an sp3 carbon to form an alkyl radical.

Visible-Light-Driven C-S Bond Formation Based on Electron Donor-Acceptor Excitation and Hydrogen Atom Transfer Combined System.

Developed herein is a visible-light-driven synthesis of sulfides by an electron donor-acceptor/single electron transfer and hydrogen atom transfer combined system without transition metals and strong oxidants. This reaction proceeds through the excitation of an electron donor-acceptor complex between a thiolate and an aryl halide, followed by the hydrogen atom transfer from an alkane to the generated aryl radical.