1. Mechanism of Enolate Transfer between Si and Cu
- Author
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Hélène Gérard, Samira Bouaouli, Emmanuel Vrancken, Jean-Marc Campagne, Kim Spielmann, Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and ANR-09-BLAN-0089,CopEnol,Caractérisation et Propriétés d'Enolates de Cuivre Conjugués(2009)
- Subjects
Silicon ,Reaction mechanism ,010405 organic chemistry ,Reaction mechanisms ,Organic Chemistry ,chemistry.chemical_element ,General Chemistry ,010402 general chemistry ,Kinetic energy ,01 natural sciences ,Copper ,Catalysis ,0104 chemical sciences ,Reaction coordinate ,Density functional calculations ,Crystallography ,chemistry ,Substituent effects ,[CHIM]Chemical Sciences ,Moiety ,Bond energy - Abstract
International audience; Exchange of X (F, Cl, OMe) and a substituted enolate chain between SiMe3 and various CuI complexes was examined. Reaction mechanisms pass through a cyclic transition state in which the reaction coordinate is associated with rotation of the SiMe3 moiety. The dependence of the thermodynamic and kinetic features on the nature of the active and ancillary ligands was examined. Formation of copper enolate is shown to be favored when stabilized enolates are used. Replacement of F by Cl reverses the preference of the reaction. This is associated with the small difference between the Cu−Cl and Si−Cl bond energies, in contrast to other Si−X bonds, which are systematically stronger than their Cu−X analogues.
- Published
- 2018
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