<i>S</i>‐Trifluoromethylation of Thiols by Hypervalent Iodine Reagents: A Joint Experimental and Computational Study

DOI Web Site Web Site 被引用文献1件
  • Oliver Sala
    Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland
  • Nico Santschi
    Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland
  • Stefan Jungen
    Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland
  • Hans Peter Lüthi
    Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland
  • Marcella Iannuzzi
    University of Zurich Department of Chemistry Winterthurerstr. 190 8057 Zürich Switzerland
  • Nicole Hauser
    Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland
  • Antonio Togni
    Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology ETH Zürich Vladimir-Prelog-Weg 2 CH-8093 Zürich Switzerland

書誌事項

公開日
2016-01-07
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/chem.201503774
公開者
Wiley

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説明

<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>

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