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Insights into the origin of selectivity for [2+2] cycloaddition step reaction involved in the mechanism of enantioselective reduction of ketones with borane catalyzed by a B-methoxy oxazaborolidine catalyst derived from (–)-β-pinene: an HMDFT and combined topological ELF, NCI and QTAIM study

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Abstract

Theoretical studies on [2+2] cycloaddition step involved in the enantioselective reduction of ketones with borane catalyzed by a B-methoxyoxazaborolidine catalyst derived from pinene have been performed by means of the hybrid meta density functional theory method at MPWB1K/6-31G (d,p). The formation of the M5a(S) complexes via transition state TSa(S) was the more favorable pathway among other [2+2] cycloaddition competing steps. The explanation of the formation of O–B and N–B through two-stage one-step mechanism was allowed by means of the electron localization function topological analysis. NCI and QTAIM analysis of the two computed transition states TSa(S) and TSa(R) indicates that the difference between both in terms of stability comes mainly from the orientation of the methanediyl group inside the pinene skeleton, which implies that CH–H…O interaction found at TSa(S) is the great factor that makes it more stable than TSa(R).

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Authors and Affiliations

  1. Laboratoire des Produits Naturels d’Origine Végétale et de Synthèse Organique, Département de Chimie, Faculté des Sciences Exactes, Université Frères Mentouri - Constantine 1, Constantine, Algeria

    Hichem Sadrik Kettouche

  2. Département de Chimie, Faculté des Sciences, Université Badji Mokhtar Annaba, BP 12, 23000, Annaba, Algeria

    Abdelhafid Djerourou

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  1. Hichem Sadrik Kettouche
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  2. Abdelhafid Djerourou
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Kettouche, H.S., Djerourou, A. Insights into the origin of selectivity for [2+2] cycloaddition step reaction involved in the mechanism of enantioselective reduction of ketones with borane catalyzed by a B-methoxy oxazaborolidine catalyst derived from (–)-β-pinene: an HMDFT and combined topological ELF, NCI and QTAIM study. Theor Chem Acc 140, 150 (2021). https://doi.org/10.1007/s00214-021-02848-4

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