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Synthesis of Phenol–Pyridinium Salts Enabled by Tandem Electron Donor–Acceptor Complexation and Iridium Photocatalysis

Matthew C. Carson, C. Liu, Marisa C. Kozlowski

2024The Journal of Organic Chemistry16 citationsDOIOpen Access PDF

Abstract

Herein, we describe a dual photocatalytic system to synthesize phenol–pyridinium salts using visible light. Utilizing both electron donor–acceptor (EDA) complex and iridium(III) photocatalytic cycles, the C–N cross-coupling of unprotected phenols and pyridines proceeds in the presence of oxygen to furnish pyridinium salts. Photocatalytic generation of phenoxyl radical cations also enabled a nucleophilic aromatic substitution (S N Ar) of a fluorophenol with an electron-poor pyridine. Spectroscopic experiments were conducted to probe the mechanism and reaction selectivity. The unique reactivity of these phenol–pyridinium salts were displayed in several derivatization reactions, providing rapid access to a diverse chemical space.

Topics & Concepts

PyridiniumChemistryPhotocatalysisPyridinePhenolIridiumPhotochemistryNucleophilic aromatic substitutionNucleophileElectron donorElectron acceptorCombinatorial chemistryInorganic chemistryNucleophilic substitutionOrganic chemistryCatalysisRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques