{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1362262944756540288.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1002/chem.201503774"}},{"identifier":{"@type":"URI","@value":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.201503774"}},{"identifier":{"@type":"URI","@value":"https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201503774"}}],"dc:title":[{"@value":"<i>S</i>‐Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:title>Abstract</jats:title><jats:p>The radical trifluoromethylation of thiophenol in condensed phase applying reagent <jats:bold>1</jats:bold> (3,3‐dimethyl‐1‐(trifluoromethyl)‐1<jats:italic>λ</jats:italic><jats:sup>3</jats:sup>,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 <jats:italic>S</jats:italic>‐centred nucleophile thiophenol, their free energies of activation, Δ<jats:italic>F</jats:italic><jats:sup>≠</jats:sup>, lying between 9 and 15 kcal mol<jats:sup>−1</jats:sup>. We further show that the origin of the proton activating the reagent is important. Hammett plot analysis reveals intramolecular protonation of <jats:bold>1</jats:bold>, thus generating negative charge on the sulfur atom in the rate‐determining step. The formation of a CF<jats:sub>3</jats:sub> radical can be thermally induced by internal dissociative electron transfer, its activation energy, Δ<jats:italic>F</jats:italic><jats:sup>≠</jats:sup>, amounting to as little as 10.8 and 2.8 kcal mol<jats:sup>−1</jats:sup> for reagent <jats:bold>1</jats:bold> and its protonated form <jats:bold>2</jats:bold>, respectively. The reduction of the iodine atom by thiophenol occurs either subsequently or in a concerted fashion.</jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1382262944756540288","@type":"Researcher","foaf:name":[{"@value":"Oliver Sala"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich  Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944756540289","@type":"Researcher","foaf:name":[{"@value":"Nico Santschi"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich  Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland"},{"@value":"Organisch Chemisches Institut Westfälische Wilhelms-Universität  Münster Corrensstrasse 40 Münster Germany"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944756540416","@type":"Researcher","foaf:name":[{"@value":"Stefan Jungen"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich  Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944756540417","@type":"Researcher","foaf:name":[{"@value":"Hans Peter Lüthi"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich  Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944756540291","@type":"Researcher","foaf:name":[{"@value":"Marcella Iannuzzi"}],"jpcoar:affiliationName":[{"@value":"University of Zurich Department of Chemistry  Winterthurerstr. 190 8057 Zürich Switzerland"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944756540292","@type":"Researcher","foaf:name":[{"@value":"Nicole Hauser"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich  Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland"}]},{"@id":"https://cir.nii.ac.jp/crid/1382262944756540290","@type":"Researcher","foaf:name":[{"@value":"Antonio Togni"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich  Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"09476539"},{"@type":"EISSN","@value":"15213765"}],"prism:publicationName":[{"@value":"Chemistry – A European Journal"}],"dc:publisher":[{"@value":"Wiley"}],"prism:publicationDate":"2016-01-07","prism:volume":"22","prism:number":"5","prism:startingPage":"1704","prism:endingPage":"1713"},"reviewed":"false","dc:rights":["http://onlinelibrary.wiley.com/termsAndConditions#vor"],"url":[{"@id":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.201503774"},{"@id":"https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201503774"}],"createdAt":"2016-01-08","modifiedAt":"2025-10-12","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/2050588892096788096","@type":"Article","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Fluoroalkylation methods for synthesizing versatile building blocks"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1002/chem.201503774"},{"@type":"CROSSREF","@value":"10.1246/bcsj.20190080_references_DOI_8ohAlLn72BIcc96ic5bTQWX7epB"}]}