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Caballero-García G, Romero-Ortega M, Barroso-Flores J. Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles. Phys Chem Chem Phys. 2016;18(39):27300-27307doi: 10.1039/c6cp04321f.
Caballero-García, G., Romero-Ortega, M., & Barroso-Flores, J. (2016). Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles. Physical chemistry chemical physics : PCCP, 18(39), 27300-27307. https://doi.org/10.1039/c6cp04321f
Caballero-García, Guillermo, et al. "Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles." Physical chemistry chemical physics : PCCP vol. 18,39 (2016): 27300-27307. doi: https://doi.org/10.1039/c6cp04321f
Caballero-García G, Romero-Ortega M, Barroso-Flores J. Reactivity of electrophilic chlorine atoms due to σ-holes: a mechanistic assessment of the chemical reduction of a trichloromethyl group by sulfur nucleophiles. Phys Chem Chem Phys. 2016 Oct 05;18(39):27300-27307. doi: 10.1039/c6cp04321f. PMID: 27722305.
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Phys Chem Chem Phys. 2016 Oct 05;18(39):27300-27307. doi: 10.1039/c6cp04321f.

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

Physical chemistry chemical physics : PCCP

Guillermo Caballero-García, Moisés Romero-Ortega, Joaquín Barroso-Flores

Affiliations

  1. Centro Conjunto de Investigación en Química Sustentable UAEM - UNAM, Carretera Toluca-Atlacomulco km 14.5, Unidad San Cayetano, Personal de la UNAM, Toluca 50200, Estado de México, Mexico. [email protected] and Facultad de Química, Universidad Autónoma del Estado de México, Paseo Colón/Paseo Tollocan, s/n, Toluca 50000, Estado de México, Mexico.
  2. Facultad de Química, Universidad Autónoma del Estado de México, Paseo Colón/Paseo Tollocan, s/n, Toluca 50000, Estado de México, Mexico.
  3. Centro Conjunto de Investigación en Química Sustentable UAEM - UNAM, Carretera Toluca-Atlacomulco km 14.5, Unidad San Cayetano, Personal de la UNAM, Toluca 50200, Estado de México, Mexico. [email protected].

PMID: 27722305 DOI: 10.1039/c6cp04321f

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

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