NDLI: S-Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study

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S-Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Jungen, Stefan Sala, Oliver Hauser, Nicole Togni, Antonio Santschi, Nico Iannuzzi, Marcella Lüthi, Hans Peter
Description	Author Affiliation: Sala O ( Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093, Zürich, Switzerland.); Santschi N ( Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093, Zürich, Switzerland.); Jungen S ( Organisch Chemisches Institut, Westfälische Wilhelms-Universität, Münster Corrensstrasse 40, Münster, Germany.); Lüthi HP ( Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093, Zürich, Switzerland.); Iannuzzi M ( Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093, Zürich, Switzerland.); Hauser N ( University of Zurich, Department of Chemistry, Winterthurerstr. 190, 8057, Zürich, Switzerland.); Togni A ( Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Zürich, Vladimir-Prelog-Weg 2, CH-8093, Zürich, Switzerland.)
Abstract	The radical trifluoromethylation of thiophenol in condensed phase applying reagent 1 $(3,3-dimethyl-1-(trifluoromethyl)-1λ^{3},2-benziodoxol)$ has been examined by both theoretical and experimental methodologies. On the basis of ab initio molecular dynamics and metadynamics we show that radical reaction mechanisms favourably compete with polar ones involving the S-centred nucleophile thiophenol, their free energies of activation, $ΔF^{≠},$ lying between 9 and $15 kcal mol^{−1}.$ We further show that the origin of the proton activating the reagent is important. Hammett plot analysis reveals intramolecular protonation of 1, thus generating negative charge on the sulfur atom in the rate-determining step. The formation of a $CF_{3}$ radical can be thermally induced by internal dissociative electron transfer, its activation energy, $ΔF^{≠},$ amounting to as little as 10.8 and $2.8 kcal mol^{−1}$ for reagent 1 and its protonated form 2, respectively. The reduction of the iodine atom by thiophenol occurs either subsequently or in a concerted fashion.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	5
Volume Number	22
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2016-01-26
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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