Predicting reactive sites with quantum chemical topology: carbonyl additions in multicomponent reactions

Quantum Chemical Topology (QCT) is a well established structural theoretical approach, but the development of its reactivity component is still a challenge. The hypothesis of this work is that the reactivity of an atom within a molecule is a function of its electronic population, its delocalization...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2020-05, Vol.22 (17), p.9283-9289
Main Authors: Ramírez-Palma, David I, García-Jacas, Cesar R, Carpio-Martínez, Pablo, Cortés-Guzmán, Fernando
Format: Article
Language:English
Subjects:
Carbonyl compounds
Carbonyls
Chemical equilibrium
Chemical reactions
Electron density
Functional groups
Quantum chemistry
Reactivity
Topology
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Summary:Quantum Chemical Topology (QCT) is a well established structural theoretical approach, but the development of its reactivity component is still a challenge. The hypothesis of this work is that the reactivity of an atom within a molecule is a function of its electronic population, its delocalization in the rest of the molecule, and the way it polarizes within an atomic domain. In this paper, we present a topological reactivity predictor for cabonyl additions, κ . It is a measure of the polarization of the electron density with the carbonyl functional group. κ is a model obtained from a QSAR procedure, using quantum-topological atomic descriptors and reported hydration equilibrium constants of carbonyl compounds. To validate the predictive capability of κ , we applied it to organic reactions, including a multicomponent reaction. κ was the only property that predicts the reactivity in each reaction step. The shape of κ can be interpreted as the change between two electrophilic states of a functional group, reactive and non-reactive. The reactivity of an atom within a molecule depends mostly on the way the electron density polarizes reflected in the quadrupole moment of the reactive atom.
ISSN:1463-9076
1463-9084
DOI:10.1039/d0cp00300j