Aza-Michael Addition in Explicit Solvent: A Relative Energy Gradient-Interacting Quantum Atoms Study.

Autor: Cador A; Normandy Univ., COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821, Mont St, Aignan Cedex, France., Tognetti V; Normandy Univ., COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821, Mont St, Aignan Cedex, France., Joubert L; Normandy Univ., COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821, Mont St, Aignan Cedex, France., Popelier PLA; Department of Chemistry, The University of Manchester, Manchester, M13 9PL, Great Britain.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2023 Dec 14; Vol. 24 (24), pp. e202300529. Date of Electronic Publication: 2023 Nov 17.
DOI: 10.1002/cphc.202300529
Abstrakt: Aza-Michael additions are key reactions in organic synthesis. We investigate, from a theoretical and computational point of view, several examples ranging from weak to strong electrophiles in dimethylsulfoxide treated as explicit solvent. We use the REG-IQA method, which is a quantum topological energy decomposition (Interacting Quantum Atoms, IQA) coupled to a chemical-interpretation calculator (Relative Energy Gradient, REG). We focus on the rate-limiting addition step in order to unravel the different events taking place in this step, and understand the influence of solvent on the reaction, with an eye on predicting the Mayr electrophilicity. For the first time, a link is established between an REG-IQA analysis and experimental values.
(© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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