CeNT Seminar (7.05.2025): Searching for the right model: The case of the nucleophilic addition from the Felkin-Anh rule to the Grignard reac6on

05 05 2025

The Centre of New Technologies, University of Warsaw invites to a seminar by:

Professor Odile Eisenstein

ICGM Université de Montpellier, CNRS ENSCM Montpellier, France

Department of Chemistry and Hylleraas Center for Quantum Molecular Sciences, University of Oslo, Norway

Title: Searching for the right model: The case of the nucleophilic addition from the Felkin-Anh rule to the Grignard reaction

Date: 7.05.2025, Wednesday

Time: 10:00 am (Central European Time)

The seminar will be held in room 00.142

Abstract:

The study of the Grignard reaction is part of our long-standing interest in the study of nucleophilic addition. Many years ago, calculations could be performed using very simplified models of the reagents.[1] These very simplified models of the chemical systems were successful in providing qualitative insights for many reactions [2]. Today, it is possible to model reactions using realistic representations of the chemical species and methods that represent properly the thermodynamics of complex systems. Thus, we have studied the Grignard reaction, a reaction in which a Grignard reagent, RMgX reacts with a carbonyl carbon by making a new C-R bond and form an alcohol after hydrolysis. This reaction, discovered in 1900 by Victor Grignard, enables the controlled formation of C-C bond and is thus essential for organic synthesis in the academic and industrial laboratories alike. It was honored by a Nobel prize in 1912. In an attempt to provide insights into a reaction, which has remained elusive despite extensive studies since its discovery in 1900, we have used ab initio molecular dynamics to study the species that are present when CH3MgCl is added to an organic solvent (tetrahydrofuran). We will present the arguments that led us to believe that the Grignard reagent is present in a large number of forms in solution [3] and that the Grignard reaction occurs via numerous parallel pathways [4]. We pursue with the presentation of the complex structures of lithium salts (LiX, X = halide) in organic solvent (5) with the goal to understand the role of additives such as LiCl [6] in the reaction (turbo-Grignard). A perspective on this topic is available (7).

[1] O. Eisenstein Isr. J. Chem. 62, e202100138 (2022)
[2] O. Eisenstein Comptes Rendus Acad. Sciences 27, Special Issue S2, 5, (2024) https://doi.org/10.5802/crchim.298
[3] R. M. Peltzer, O. Eisenstein, A. Nova, M. Cascella J. Phys. Chem. B 121, 4226 (2017)
[4] R. M. Peltzer, J. Gauss, O. Eisenstein, M. Cascella J. Am. Chem. Soc. 142, 2984 (2020)
[5] M. de Giovanetti, S. H. Hopen Eliasson, S. L. Bore, O. Eisenstein, M. Cascella Chem. Sci., 15, 20355 (2024)
[6] M. de Giovanetti, S. H. Hopen Eliasson, A. C. Castro, O. Eisenstein, M. Cascella J. Am. Chem. Soc. 145, 16305 (2023)
[7] M. Cascella, S. L. Bore, O. Eisenstein Chem. Sci. https://doi.org/10.1039/D5SC01078K