We report using visible-light-induced generation of tether-tunable distonic radical anions for the general catalytic lactonization/lactamization of aromatic carboxylic acids and benzamides. Its success relies on the specific cyclic diacyl peroxide and catalytic amount of CsI, enabling the generation of electrophilic heteroatom-centered radicals via a philicity regulation strategy. Key features include operational simplicity, excellent functional group tolerance, broad substrate scope, high chemo- and regioselectivity, gram-scale scalability, and application to synthesis of urolithin derivatives and 3--butylphthalide.
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A Unified Approach to Lactonization/Lactamization by Leveraging Tether-Tunable Distonic Radical Anions.
Org Lett
March 2025
School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China.
We report using visible-light-induced generation of tether-tunable distonic radical anions for the general catalytic lactonization/lactamization of aromatic carboxylic acids and benzamides. Its success relies on the specific cyclic diacyl peroxide and catalytic amount of CsI, enabling the generation of electrophilic heteroatom-centered radicals via a philicity regulation strategy. Key features include operational simplicity, excellent functional group tolerance, broad substrate scope, high chemo- and regioselectivity, gram-scale scalability, and application to synthesis of urolithin derivatives and 3--butylphthalide.
View Article and Find Full Text PDFRevealing the nature of covalently tethered distonic radical anions in the generation of heteroatom-centered radicals: evidence for the polarity-matching PCET pathway.
Chem Sci
August 2024
School of Chemistry and Chemical Engineering, School of Science(shenzhen), Harbin Institute of Technology Harbin 150001 China
Recognition of the intermediacy and regulation of reactivity patterns of radical intermediates in radical chemistry have profound impacts on harnessing and developing the full potential of open-shell species in synthetic settings. In this work, the possibility of formation of O/N-X intermediates from Brønsted base covalently tethered carbonyl hypohalites (BCTCs) for the generation of heteroatom-centered radicals has certainly been excluded by NMR experiments and density functional theory calculations. Instead, the spectroscopic analyses reveal that the BCTCs serve as precursors of tether-tunable distonic radical anions (TDRAs) which have been unequivocally substantiated to be involved in the direct cleavage of O/N-H bonds to generate the corresponding heteroatom-centered radicals.
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