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Article Dans Une Revue Tetrahedron Année : 2012

Intramolecular homolytic substitution of seleninates - a computational study

Anne C. Neves
  • Fonction : Auteur
Heather M. Aitken
  • Fonction : Auteur
Sara H. Kyne
  • Fonction : Auteur
Louis Fensterbank
Emmanuel Lacôte
Max Malacria
Cyril Ollivier
Carl H. Schiesser
  • Fonction : Auteur

Résumé

Ab initio and density functional theory (DFT) calculations predict that intramolecular homolytic substitution by alkyl radicals at the selenium atom in seleninates proceeds through smooth transition states in which the attacking and leaving radicals adopt a near collinear arrangement. When forming a five-membered ring and the leaving radical is methyl. G3(MP2)-RAD calculations predict that this reaction proceeds with an activation energy (Delta E(1)(t)) of 30.4 kJ mol(-1). ROBHandHLYP/6-311++G(d,p) calculations suggest that the formation of five-membered rings through similar intramolecular homolytic substitution by aryl radicals, with expulsion of phenyl radicals, proceeds with the involvement of a hyper-valent intermediate. This intermediate further dissociates to the observed products, with overall energy barriers of about 40 kJ mol(-1). Homolytic addition to the phenyl group was found not to be competitive with substitution, with a calculated barrier of 57.6 kJ mol(-1). This computational study provides insight into homolytic substitution chemistry involving seleninates.

Dates et versions

hal-01397622 , version 1 (16-11-2016)

Identifiants

Citer

Anne C. Neves, Heather M. Aitken, Sara H. Kyne, Louis Fensterbank, Emmanuel Lacôte, et al.. Intramolecular homolytic substitution of seleninates - a computational study. Tetrahedron, 2012, 68 (1), pp.323-328. ⟨10.1016/j.tet.2011.10.037⟩. ⟨hal-01397622⟩
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