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A Quantification Scheme for Non-covalent Interactions in the Enantio-controlling Transition States in Asymmetric Catalysis

Abstract

The origin of enantioselectivity in asymmetric catalysis is attributed to the energy difference between the lower and the higher energy diastereomeric transition states, respectively responsible for the formation of the major and minor enantiomers. Although increasing number of transition state models now emphasize on the role of weak non-covalent interactions in asymmetric induction, the strength of such interactions are seldom quantified. Through this article, we propose a simple and effective method to quantify the total non-covalent interaction in the stereocontrolling transition states belonging to a group of three representative asymmetric catalytic reactions involving chiral phosphoric acids. Our method relies on rational partitioning of a given transition state into two (or three) sub-units such that the complex network of intramolecular interactions could be ameliorated to a set of intermolecular interactions between two sub-units. The computed strength of interaction obtained using the counter-poise (CP) method offers improved estimates of non-covalent interactions and are also devoid of basis set superposition error (BSSE). It has been noted that the catalysts decorated with larger aromatic arms can provide a cumulative non-covalent interaction (C–H∙∙∙π, N–H∙∙∙π and π∙∙∙π) to the tune of 10 to 15 kcal/mol. Fine-tuning the magnitude and nature of these interaction could provide valuable avenues in the design of asymmetric catalysts.

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Publication details

The article was received on 17 May 2018, accepted on 12 Jul 2018 and first published on 12 Jul 2018


Article type: Paper
DOI: 10.1039/C8OB01158C
Citation: Org. Biomol. Chem., 2018, Accepted Manuscript
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    A Quantification Scheme for Non-covalent Interactions in the Enantio-controlling Transition States in Asymmetric Catalysis

    S. V. S. Sowndarya, S. Malakar and R. B. Sunoj, Org. Biomol. Chem., 2018, Accepted Manuscript , DOI: 10.1039/C8OB01158C

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