A molecular-wide and electron density-based approach in exploring chemical reactivity and explicit dimethyl sulfoxide (DMSO) solvent molecule effects in the proline catalyzed aldol reaction

dc.contributor.authorCukrowski, Ignacy
dc.contributor.authorDhimba, George
dc.contributor.authorRiley, Darren Lyall
dc.contributor.emailignacy.cukrowski@up.ac.zaen_US
dc.date.accessioned2023-09-21T09:13:06Z
dc.date.available2023-09-21T09:13:06Z
dc.date.issued2022-01-31
dc.descriptionThe Supporting Information is available free of charge as Cartesian XYZ coordinates of molecular systems and their energies; selected geometric data; net atomic charges; inter-fragment interaction energies; reaction energy profiles.en_US
dc.descriptionDATA AVAILABILITY STATEMENT : On request, computational data are available from I.C.en_US
dc.description.abstractModelling of the proline (1) catalyzed aldol reaction (with acetone 2) in the presence of an explicit molecule of dimethyl sulfoxide (DMSO) (3) has showed that 3 is a major player in the aldol reaction as it plays a double role. Through strong interactions with 1 and acetone 2, it leads to a significant increase of energy barriers at transition states (TS) for the lowest energy conformer 1a of proline. Just the opposite holds for the higher energy conformer 1b. Both the ‘inhibitor’ and ‘catalyst’ mode of activity of DMSO eliminates 1a as a catalyst at the very beginning of the process and promotes the chemical reactivity, hence catalytic ability of 1b. Modelling using a Molecular-Wide and Electron Density-based concept of Chemical Bonding (MOWED-CB) and the Reaction Energy Profile–Fragment Attributed Molecular System Energy Change (REP-FAMSEC) protocol has shown that, due to strong intermolecular interactions, the HN-C-COOH (of 1), CO (of 2), and SO (of 3) fragments drive a chemical change throughout the catalytic reaction. We strongly advocate exploring the pre-organization of molecules from initially formed complexes, through local minima to the best structures suited for a catalytic process. In this regard, a unique combination of MOWED-CB with REP-FAMSEC provides an invaluable insight on the potential success of a catalytic process, or reaction mechanism in general. The protocol reported herein is suitable for explaining classical reaction energy profiles computed for many synthetic processes.en_US
dc.description.departmentChemistryen_US
dc.description.librarianam2023en_US
dc.description.sponsorshipThe National Research Foundation of South Africa.en_US
dc.description.urihttps://www.mdpi.com/journal/moleculesen_US
dc.identifier.citationCukrowski, I.; Dhimba, G.; Riley, D.L. A Molecular-Wide and Electron Density-Based Approach in Exploring Chemical Reactivity and Explicit Dimethyl Sulfoxide (DMSO) Solvent Molecule Effects in the Proline Catalyzed Aldol Reaction. Molecules 2022, 27, 962. https://DOI.org/10.3390/molecules27030962.en_US
dc.identifier.issn1420-3049 (online)
dc.identifier.other10.3390/molecules27030962
dc.identifier.urihttp://hdl.handle.net/2263/92370
dc.language.isoenen_US
dc.publisherMDPIen_US
dc.rights© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license.en_US
dc.subjectProline catalyzed aldol reactionen_US
dc.subjectReaction mechanismen_US
dc.subjectExplicit solvent effectsen_US
dc.subjectREP-FAMSEC Methoden_US
dc.subjectChemical reactivityen_US
dc.subjectForces driving a chemical changeen_US
dc.subjectDimethyl sulphide (DMSO)en_US
dc.titleA molecular-wide and electron density-based approach in exploring chemical reactivity and explicit dimethyl sulfoxide (DMSO) solvent molecule effects in the proline catalyzed aldol reactionen_US
dc.typeArticleen_US

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