<i>meso</i>-Tetraphenylporphyrin Iron Chloride Catalyzed Selective Oxidative Cross-Coupling of Phenols

A novel catalytic system for oxidative cross-coupling of readily oxidized phenols with poor nucleophilic phenolic partners based on an iron <i>meso</i>-tetraphenylporphyrin chloride (Fe­[TPP]­Cl) complex in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) was developed. The unique chemoselectivity of this reaction is attributed to the coupling between a liberated phenoxyl radical with an iron-ligated phenolic coupling partner. The conditions are scalable for preparing a long list of unsymmetrical biphenols assembled from a less reactive phenolic unit substituted with alkyl or halide groups

Synthetic and Predictive Approach to Unsymmetrical Biphenols by Iron-Catalyzed Chelated Radical–Anion Oxidative Coupling

An iron-catalyzed oxidative unsymmetrical biphenol coupling in 1,1,1,3,3,3-hexafluoropropan-2-ol that proceeds via a chelated radical–anion coupling mechanism was developed. Based on mechanistic studies, electrochemical methods, and density functional theory calculations, we suggest a general model that enables prediction of the feasibility of cross-coupling for a given pair of phenols

Synthetic and Predictive Approach to Unsymmetrical Biphenols by Iron-Catalyzed Chelated Radical–Anion Oxidative Coupling

An iron-catalyzed oxidative unsymmetrical biphenol coupling in 1,1,1,3,3,3-hexafluoropropan-2-ol that proceeds via a chelated radical–anion coupling mechanism was developed. Based on mechanistic studies, electrochemical methods, and density functional theory calculations, we suggest a general model that enables prediction of the feasibility of cross-coupling for a given pair of phenols