Transition‐Metal‐Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate. Issue 51 (22nd November 2017)

• Record Type: Journal Article
• Authors: Kikushima, Kotaro; Grellier, Mary; Ohashi, Masato; Ogoshi, Sensuke
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 51(2017)
• Page Start: 16191
• Page End: 16196
• Publication Date: 2017-11-22
• Subjects: defluorination -- fluoroarenes -- hydride transfer -- nucleophilic aromatic substitution -- silicates; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201708003
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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 (CSN Ar) process. Abstract : A simple but artful combination : Transition‐metal‐free catalytic hydrodefluorination (HDF) of polyfluoroarenes was enabled by a hydrosilicate catalyst formed in situ from a hydrosilane and a fluoride ion. The reaction involves direct hydride transfer from the hydrosilicate through concerted nucleophilic aromatic substitution (CSN Ar; see scheme).