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Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects
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SYSNO ASEP 0507252 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Preparation of (Pentafluorosulfanyl)benzenes by Direct Fluorination of Diaryldisulfides: Synthetic Approach and Mechanistic Aspects Author(s) Ajenjo, Javier (UOCHB-X)
Klepetářová, Blanka (UOCHB-X) RID, ORCID
Greenhall, M. (GB)
Bím, Daniel (UOCHB-X) ORCID, RID
Culka, Martin (UOCHB-X) ORCID
Rulíšek, Lubomír (UOCHB-X) RID, ORCID
Beier, Petr (UOCHB-X) RID, ORCIDSource Title Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 25, č. 48 (2019), s. 11375-11382Number of pages 8 s. Language eng - English Country DE - Germany Keywords fluorine ; pentafluorosulfanyl ; radical reactions ; reaction mechanisms ; synthetic methods Subject RIV CC - Organic Chemistry OECD category Organic chemistry R&D Projects GC18-00215J GA ČR - Czech Science Foundation (CSF) Method of publishing Limited access Institutional support UOCHB-X - RVO:61388963 UT WOS 000479224000001 EID SCOPUS 85070676635 DOI https://doi.org/10.1002/chem.201902651 Annotation 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. Workplace Institute of Organic Chemistry and Biochemistry Contact asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Year of Publishing 2020 Electronic address https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201902651
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