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.
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.
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 from alkanes. 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 a Minisci-type addition of alkyl radicals 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 alkane to form an alkyl radical.
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 from alkanes. 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 a Minisci-type addition of alkyl radicals 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 alkane to form an alkyl radical.
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