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Phosphinylation of Non‐activated Aryl Fluorides through Nucleophilic Aromatic Substitution at the Boundary of Concerted and Stepwise Mechanisms
Author(s) -
You Zhensheng,
Higashida Kosuke,
Iwai Tomohiro,
Sawamura Masaya
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013544
Subject(s) - chemistry , nucleophile , aryl , concerted reaction , medicinal chemistry , nucleophilic substitution , phosphine , nucleophilic aromatic substitution , substitution reaction , reaction mechanism , radical nucleophilic aromatic substitution , photochemistry , organic chemistry , catalysis , alkyl
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.