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Issue 39, 2016
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Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles

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Abstract

σ-Holes are shown to promote the electrophilic behavior of chlorine atoms in a trichloromethyl group when bound to an electron-withdrawing moiety. A halogen bond-type non-covalent interaction between a chlorine atom and a negatively charged sulfur atom takes place, causing the abstraction of such a chlorine atom while leaving a carbanion, subsequently driving the chemical reduction of the trichloromethyl group to a sulfide in a stepwise process. The mechanism for the model reaction of trichloromethyl pyrimidine 1 with thiophenolate and thiophenol to yield phenylsulfide 4 was followed through 1H-NMR and studied using DFT transition state calculations, and the energy profile for this transformation is fully discussed. MP2 calculations of the electrostatic potential were performed for a series of trichloromethyl compounds in order to assess the presence of σ-holes and quantify them by means of the maximum surface electrostatic potential. Such calculations showed that the chlorine atoms behave as electrophilic leaving groups toward a nucleophilic attack, opening a new possibility in the synthetic chemistry of the trichloromethyl group.

Graphical abstract: Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles

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Publication details

The article was received on 20 Jun 2016, accepted on 05 Sep 2016, published on 05 Sep 2016 and first published online on 05 Sep 2016


Article type: Paper
DOI: 10.1039/C6CP04321F
Citation: Phys. Chem. Chem. Phys., 2016,18, 27300-27307
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    Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles

    G. Caballero-García, M. Romero-Ortega and J. Barroso-Flores, Phys. Chem. Chem. Phys., 2016, 18, 27300
    DOI: 10.1039/C6CP04321F

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