title: Photocatalytic Anion Oxidation and Applications in Organic Synthesis.
abstract: Ions and radicals of the same kind differ by one electron only. The oxidation of many stable inorganic anions yields their corresponding highly reactive radicals, and visible light excitable photocatalysts can provide the required oxidation potential for this transformation. Air oxygen serves as the terminal oxidant, or cheap sacrificial oxidants are used, providing a very practical approach for generating reactive inorganic radicals for organic synthesis. We discuss in this perspective several recently reported examples: Nitrate radicals are obtained by one-electron photooxidation of nitrate anions and are very reactive toward organic molecules. The photooxidation of sulfinate salts yields the much more stable sulfone radicals, which smoothly add to double bonds. A two-electron oxidation of chloride anions to electrophilic chlorine species reacting with arenes in aromatic substitutions extends the method beyond radical reactions. The chloride anion oxidation proceeds via photocatalytically generated peracidic acid as the oxidation reagent. Although the number of reported examples of photocatalytically generated inorganic radical intermediates for organic synthesis is still small, future extension of the concept to other inorganic ions as radical precursors is a clear perspective.
authors.affiliation: Institute of Organic Chemistry, Faculty of Chemistry and Pharmacy, University of Regensburg , D-93040 Regensburg, Germany.
authors.forename: Thea
authors.initials: T
authors.lastname: Hering
authors.affiliation: Institute of Organic Chemistry, Faculty of Chemistry and Pharmacy, University of Regensburg , D-93040 Regensburg, Germany.
authors.forename: Andreas Uwe
authors.initials: AU
authors.lastname: Meyer
authors.affiliation: Institute of Organic Chemistry, Faculty of Chemistry and Pharmacy, University of Regensburg , D-93040 Regensburg, Germany.
authors.forename: Burkhard
authors.initials: B
authors.lastname: König