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Article Dans Une Revue Chemistry - A European Journal Année : 2011

Evidences for the Key Role of Hydrogen Bonds in Nucleophilic Aromatic Substitution Reactions

Laurent El Kaim
Laurence Grimaud
Paul Fleurat-Lessard

Résumé

The effect of hydrogen bonds on the fate of nucleophilic aromatic substitutions (SNAr) has been studied in silico using a density functional theory approach in the condensed phase. The importance of these hydrogen bonds can explain the “built-in solvation” model of Bunnett concerning intermolecular processes between halogenonitrobenzenes and amines. It is also demonstrated that it can explain experimental results for a multicomponent reaction (the Ugi–Smiles coupling), involving an intramolecular SNAr (the Smiles rearrangement) as the key step of the process. Modeling reveals that when an intramolecular hydrogen bond is present, it lowers the activation barrier of this step and enables the multicomponent reaction to proceed.

Dates et versions

hal-01116254 , version 1 (12-02-2015)

Identifiants

Citer

Nicolas Chéron, Laurent El Kaim, Laurence Grimaud, Paul Fleurat-Lessard. Evidences for the Key Role of Hydrogen Bonds in Nucleophilic Aromatic Substitution Reactions. Chemistry - A European Journal, 2011, 17 (52), pp.14929-14934. ⟨10.1002/chem.201102463⟩. ⟨hal-01116254⟩
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