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On the Stability of Disubstituted Cyclobutenes - A Computational Study.

ABSTRACT: A computational study of the electrocyclic ring-opening of 2-substituted cyclobutenecarboxylic acids is presented. Detailed calculations suggest a model to predict whether the product of nucleophilic alkylation of a bicyclic lactone electrophile will be a cyclobutenecarboxylic acid or its dienoic acid isomer, based on the used nucleophile.

SUBMITTER: Maryasin B

PROVIDER: S-EPMC6472590 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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On the Stability of Disubstituted Cyclobutenes - A Computational Study.

Maryasin Boris B Maulide Nuno N

European journal of organic chemistry 20181121 2-3

A computational study of the electrocyclic ring-opening of 2-substituted cyclobutenecarboxylic acids is presented. Detailed calculations suggest a model to predict whether the product of nucleophilic alkylation of a bicyclic lactone electrophile will be a cyclobutenecarboxylic acid or its dienoic acid isomer, based on the used nucleophile. ...[more]

PMID: 31007572

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Project description:This work presents the study of a series of electrocyclic reactions with the main aim of obtaining new insights into the reaction process along IRCs. The energy variation of the different reaction paths as well as the different transition states have been calculated. These trends are according to the experimental data. The natural bond orbitals have been obtained and the second order perturbational theory analysis has been carried out to determine the main charge transfers due to delocalization. Bond reactivity indexes have been used to describe the reactivity mechanism in a local way. These reactivity indexes are also based on NBOs and this has made it possible to connect the results of the indexes with the previous analysis. To determine quantitatively the bond structure, we used the quantum theory of atoms in molecules and we have hereby completed the information obtained from the NBO analysis. Finally, we used the Hirshfeld population analysis as an approximation to understand how the load density changes in the different reaction pathways, and we have connected these variations with the information obtained from the bond structure. The results has found that the reaction path with the lowest energy barrier Transition State Inward Conrotatory (TSIC) or Transition State Outward Conrotatory (TSOC) is determined by two magnitudes: the charge donations by delocalisation of the substituents (which we obtained from the Second Order Perturbational Theory Analysis of the NBOs) and in the case that these donations were very similar, the non-covalent interactions dominated (which we studied by means of the interaction energies of the Hirshfeld charges). Additionality, the most important factor influencing the lower energy reaction path was the interaction of lone pairs of the substituents with the σ∗(C-C) bond that is broken at the opening of the cycle. The alignment of these lone pairs with the C-C bond favours charge donation between them and, as can be seen in the discussion, this alignment varies depending on whether the structure is TSIC and TSOC.

Dataset Information

On the Stability of Disubstituted Cyclobutenes - A Computational Study.

Publications

On the Stability of Disubstituted Cyclobutenes - A Computational Study.

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