Radical Anion Promoted Chemoselective Cleavage of Csp<sup>2</sup>–S Bond Enables Formal Cross-Coupling of Aryl Methyl Sulfones with Alcohols
Jixiang Bai, Tianxin Wang, Botao Dai, Qingchao Liu, Peiyuan Yu, Tiezheng Jia
Abstract
A novel formal cross-coupling of aryl methyl sulfones and alcohols affording alkyl aryl ethers via an SRN1 pathway is developed. Two marketed antitubercular drugs were efficiently prepared employing this approach as the key step. A dimsyl-anion initiated radical chain process was revealed as the major pathway. DFT calculations indicate that the formation of a radical anion via nucleophilic addition of alkoxide to the aryl radical is the key step in determining the observed chemoselectivity.
Topics & Concepts
ChemistryChemoselectivityArylAlkoxideAlkylNucleophileBond cleavageMedicinal chemistryIonAlcoholCombinatorial chemistryOrganic chemistryCatalysisSulfur-Based Synthesis TechniquesRadical Photochemical ReactionsCatalytic C–H Functionalization Methods