Pan, LeiCooke, MariaSpencer, AmaraLaulhé, Sébastien2022-02-022022-02-022022-01Pan, L., Cooke, M., Spencer, A., & Laulhé, S. (2022). Dimsyl Anion Enables Visible‐Light‐Promoted Charge Transfer in Cross‐Coupling Reactions of Aryl Halides. Advanced Synthesis & Catalysis, 364(2), 420–425. https://doi.org/10.1002/adsc.2021010521615-4150, 1615-4169https://hdl.handle.net/1805/27657A methodology is reported for visible-light-promoted synthesis of unsymmetrical chalconides enabled by dimsyl anion in the absence of transition-metals or photoredox catalysts. The cross-coupling reaction between aryl halides and diaryl dichalconides proceeds with electron-rich, electron-poor, and heteroaromatic moieties. Mechanistic investigations using UV−Vis spectroscopy, time-dependent density functional theory (TD-DFT) calculations, and control reactions suggest that dimsyl anion forms an electron-donor-acceptor (EDA) complex capable of absorbing blue light, leading to a charge transfer responsible for generation of aryl radicals from aryl halides. This previously unreported mechanistic pathway may be applied to other light-induced transformations performed in DMSO in the presence of bases and aryl halides.en-USPublisher PolicyCross-couplingDimsyl-anionPhoto-inducedTransition-metal-freeArticle