Article Dans Une Revue Nature Synthesis Année : 2024

Divergence of catalytic systems in the zinc-catalysed alkylation of benzaldehyde mediated by chiral proline-based ligands

Résumé

Asymmetric catalysis has expanded the range of chiral products readily accessible through increasingly efficient synthetic catalysts. The development of these catalysts often starts with a result obtained by systematic screening of known privileged chiral structures and assumes that the active species would be an isolated monomolecular species. Here, we report the study of three proline-derived ligands, diphenyl-N-methyl-prolinol, diphenylprolinol and 5-(hydroxydiphenylmethyl)-2-pyrrolidinone in the zinc-catalysed alkylation of benzaldehyde. The three ligands exhibit different system-level behaviour, characterised by multiple levels of aggregation that may be catalytically active simultaneously. While diphenyl-N-methyl-prolinol behaves as expected from a mechanistic point of view, diphenylprolinol shows enantiodivergence during the reaction due to an asymmetric autoinduction process. With 5-(hydroxydiphenylmethyl)-2-pyrrolidinone, we were able to establish the possibility of at least trimeric active species in equilibrium with less aggregated active species. Simulations using a mathematical model confirm the possibility of such systems-level behaviour. Parallel study of the three systems reveals three distinct system-level behaviours that are central to the efficiency of the catalytic reaction.

Domaines

Chimie Catalyse
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Dates et versions

hal-04681637 , version 1 (29-08-2024)

Identifiants

Citer

Thibault Thierry, Yannick Geiger, Stéphane Bellemin-Laponnaz. Divergence of catalytic systems in the zinc-catalysed alkylation of benzaldehyde mediated by chiral proline-based ligands. Nature Synthesis, 2024, 3 (5), pp.615-622. ⟨10.1038/s44160-024-00491-y⟩. ⟨hal-04681637⟩
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