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Transition‐Metal‐Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate
Author(s) -
Kikushima Kotaro,
Grellier Mary,
Ohashi Masato,
Ogoshi Sensuke
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201708003
Subject(s) - chemistry , photochemistry , nucleophilic aromatic substitution , nucleophilic substitution , catalysis , nucleophile , fluoride , hydride , transition metal , medicinal chemistry , inorganic chemistry , metal , organic chemistry
A transition‐metal‐free catalytic hydrodefluorination (HDF) reaction of polyfluoroarenes is described. The reaction involves direct hydride transfer from a hydrosilicate as the key intermediate, which is generated from a hydrosilane and a fluoride salt. The eliminated fluoride regenerates the hydrosilicate to complete the catalytic cycle. Dispersion‐corrected DFT calculations indicated that the HDF reaction proceeds through a concerted nucleophilic aromatic substitution (CS N Ar) process.