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Enantiodivergent Non-Linear Effects in Asymmetric Catalysis

preprint
revised on 08.09.2020 and posted on 08.09.2020 by Yannick Geiger, thierry achard, aline maisse-françois, Stephane Bellemin-Laponnaz
In this paper, we theoretically discuss the enantiodivergent product formation in asymmetric catalysis, a process in which the sign of the overall product enantiomer switches upon a change of catalyst concentration. The presented model is based on a catalytic system that consists of both discrete and dimeric aggregated metal complexes, in competition and in equilibrium. These concepts were then expanded to a non-enantiopure catalyst, giving rise to enantiodivergent non-linear effects – a special case of a hyperpositive non-linear effects where the product enantiomer’s sign switches upon a change of the catalyst enantiomeric excess. Different cases are considered allowing a discussion of the influence of the parameters governing both models. Finally, we present experimental results that support the enantiodivergence while varying the concentration of enantiopure catalyst or while varying the enantiomeric excess of the catalyst, using chiral N-methylephedrine as a ligand for the enantioselective addition of dimethylzinc to benzaldehyde.

Funding

Labex NIE ANR-11-LABX-0058_NIE

History

Email Address of Submitting Author

bellemin@unistra.fr

Institution

CNRS - Université de Strasbourg

Country

FRANCE

ORCID For Submitting Author

0000-0001-9462-5703

Declaration of Conflict of Interest

No conflict of interest

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