Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects. Issue 48 (5th August 2019)

• Record Type: Journal Article
• Authors: Ajenjo, Javier; Klepetářová, Blanka; Greenhall, Martin; Bím, Daniel; Culka, Martin; Rulíšek, Lubomír; Beier, Petr
• Is Part Of: Chemistry. Volume 25:Issue 48(2019)
• Page Start: 11375
• Page End: 11382
• Publication Date: 2019-08-05
• Subjects: fluorine -- pentafluorosulfanyl -- radical reactions -- reaction mechanisms -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201902651
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Direct fluorination of ortho ‐, meta ‐ and para ‐substituted aromatic thiols and disulfides using elemental fluorine afforded substituted (pentafluorosulfanyl)benzenes. This work thus represents the first study of the scope and limitation of direct fluorination for the synthesis of new SF5 ‐containing building blocks. Fluorinations in batch and flow modes were compared. A comprehensive computational study was carried out employing density functional and wave function methods to elucidate the reaction mechanism of the transformation of ArSF3 into ArSF5 . Eliminating various nonradical pathways, it has been shown that the reaction proceeds by a radical mechanism, initiated by the attack of the F . on the ArSF3 moiety, propagated via an almost barrierless F2 +ArSF4 . →ArSF5 +F . step and terminated by the ArSF4 . +F . →ArSF5 . Most of the calculated data are in very good agreement with experimental observations concerning the ortho ‐substituent effect on the reaction rates and yields. Abstract : Taking the direct route : Direct fluorination of substituted aromatic disulfides or thiols provided arylsulfur pentafluorides (see scheme). The scope and limitation of the direct fluorination for the synthesis of new SF5 ‐containing building blocks is described. The mechanism of the second step was investigated computationally.