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Photoinduced Iron-Catalyzed Aryl Ester Synthesis via C(sp<sup>2</sup>)-O Cross-Coupling of Carboxylic Acids with Anisoles

Jaya Tripathi, Anuj Sharma

2025ACS Catalysis5 citationsDOI

Abstract

An efficient method for the synthesis of aryl esters was developed using photoinduced iron catalysis. The carboxylation of abundantly available anisoles proceeds via an aromatic radical substitution pathway. A broad range of carboxylic acids and anisoles were successfully coupled to afford aryl esters in moderate to good yields. Mechanistic studies revealed that (i) Fe(III) is reduced to Fe(II) along with the generation of a chloride radical through a visible-light-induced ligand-to-metal charge transfer (LMCT) process; (ii) the carboxy radical is formed via hydrogen atom transfer (HAT) from the carboxylic acid to the chloride radical; (iii) Fe(III) promotes ipso -substitution by interacting with the electronegative oxygen atom of the anisole to facilitate the aryl esters synthesis.

Topics & Concepts

ChemistryAnisoleArylAryl radicalCarboxylationCatalysisChlorideCarboxylic acidOrganic chemistryHydrogen chlorideHydrogen atomMedicinal chemistryOxygen atomPhotochemistryOxygenAcyl chlorideDiazoRadicalReaction mechanismRadical substitutionRadical cyclizationRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesCatalytic C–H Functionalization Methods
Photoinduced Iron-Catalyzed Aryl Ester Synthesis via C(sp<sup>2</sup>)-O Cross-Coupling of Carboxylic Acids with Anisoles | Litcius