Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects

0507252 - ÚOCHB 2020 RIV DE eng J - Journal Article
Ajenjo, Javier - Klepetářová, Blanka - Greenhall, M. - Bím, Daniel - Culka, Martin - Rulíšek, Lubomír - Beier, Petr
Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects.
Chemistry - A European Journal. Roč. 25, č. 48 (2019), s. 11375-11382. ISSN 0947-6539. E-ISSN 1521-3765
R&D Projects: GA ČR(CZ) GC18-00215J
EU Projects: European Commission(XE) 607787 - FLUOR21
Institutional support: RVO:61388963
Keywords : fluorine * pentafluorosulfanyl * radical reactions * reaction mechanisms * synthetic methods
OECD category: Organic chemistry
Impact factor: 4.857, year: 2019
Method of publishing: Limited access
https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201902651

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 has been carried out employing density functional and wave functions methods to elucidate the reaction mechanism of the transformation of ArSF3 to ArSF5. Eliminating various non‐radical 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 almost barrier‐less F2 + ArSF4· → ArSF5 + F· step and terminated by the ArSF4· + F· → ArSF5. Most of the calculated data are in a very good agreement with experimental observations concerning the ortho‐substituent effect on the reaction rates and yields.
Permanent Link: http://hdl.handle.net/11104/0298277