Phosphinylation of Non‐activated Aryl Fluorides through Nucleophilic Aromatic Substitution at the Boundary of Concerted and Stepwise Mechanisms
Zhensheng You, Kosuke Higashida, Tomohiro Iwai, Masaya Sawamura
Abstract
Abstract Non‐activated aryl fluorides reacted with potassium diorganophosphinites through a nucleophilic aromatic substitution (S N Ar) reaction. Remarkably, both electron‐neutral and electron‐rich aryl fluorides participated in the reaction with substantially stabilized anionic P nucleophiles to form the corresponding tertiary phosphine oxides. Quantum chemical calculations suggested a nucleophile‐dependent mechanism that involves both concerted and stepwise S N Ar reaction pathways.
Topics & Concepts
ChemistryNucleophileArylConcerted reactionMedicinal chemistryRadical-nucleophilic aromatic substitutionNucleophilic substitutionNucleophilic aromatic substitutionPhosphineReaction mechanismSubstitution reactionPhotochemistryOrganic chemistryCatalysisAlkylFluorine in Organic ChemistryOrganophosphorus compounds synthesisSynthesis and characterization of novel inorganic/organometallic compounds