Computational Studies of the Reactivity, Regio-Selectivity and Stereo-Selectivity of Pericyclic Diels-Alder Reactions of Substituted Cyclobutenones

Tia, Richard

doi:10.4172/2376-130x.1000114

Cited by 5 publications

(4 citation statements)

References 29 publications

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“…The nine different dienes ( Dn-2 to Dn-10 ) were chosen based on mono and multiple substitutions of Me, OMe, and OTBS groups (Scheme ). It is well-understood that the endo adduct is more favored than that of the exoadduct both experimentally and theoretically − and thus further discussions are mainly concerned about endoadduct formation.…”

Section: Resultsmentioning

confidence: 99%

“…These types of reactions attracted more attention to its mechanistic elucidation. Further, the experimental studies done by Danishefsky suggest that the dienophile reactivity gets enhanced by incorporation of a vinyl bromide or chloride at the α-position of cyclobutenone. , Several theoretical attempts were put forth by many researchers to understand the reactivity aspects of DA reactions involving simple diene and dienophile using various levels of theory. − Notably, the Richard Tia group investigated the regio and stereoselectivity of DA reactions of chloro, cyano, methyl, and hydroxy substitution in the second, third, and fourth positions of cyclobutenones at the MP2/6-31g* level of theory. Also, they have shown the versatile role of Lewis acid catalysts in cyclobutenone involving intermolecular Diels–Alder reactions (IMDA) for enhancing the selective formation of endo product.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of Steric Effect Influence on Reactivity of Substituted Butadienes with Bromocyclobutenone

Adilakshmi

Kumar²,

Jaccob³

et al. 2019

J. Chem. Inf. Model.

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The Diels–Alder reaction (DA) between various mono- and disubstituted 1,3-butadiene (Dn-1 to Dn-10) and 2-bromocyclobutenone (DPh) was carried out in gas phase using density functional theory (DFT) at the M06-2X/6-31+g** level. The reaction was found to proceed through a concerted asynchronous transition state. Further, the asynchronous and early nature of the transition state was clearly pinpointed with the frontier molecular orbital (FMO) and bond order index (BOI) analyses. The intermolecular hydrogen bonding interaction along with steric encumbrance in the transition state were found to be the predominant factors in controlling the reactivity of the dienes. Among the investigated dienes, Dn-6 was found to be the most reactive diene which is attributed to its low activation barrier due to the presence of strong intermolecular H-bonding interactions. These factors were further supported by quantum mechanical calculations using global descriptor indexes, natural bond orbital analysis, and quantum theory of atoms in molecules analysis. These theoretical results were found to be in good agreement with the previous experimental findings.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of Steric Effect Influence on Reactivity of Substituted Butadienes with Bromocyclobutenone

Adilakshmi

Kumar²,

Jaccob³

et al. 2019

J. Chem. Inf. Model.

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“…In this case, considering the formed adduct, the presence of the electron-withdrawing nitro group in the alkene favors the expected β substitution, and the following cycloaddition follows the "ortho principle" of the Diels-Alder reaction. [19][20][21] Scheme 3. Proposed mechanism for the formation of benzodithiaporphyrin 6.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of β‐Substituted meso‐Tetraaryl‐21,23‐dithiaporphyrins by Heck Reaction

et al. 2015

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“…It was found that these particular dienophiles are very electrophilic compounds, resulting in an increase of the DA transition state asynchronicity. Another computational study, carried out by Tia et al 18 showed that maleic anhydride is a far better dienophile than cyclobutenone. This suggests that ring strain is not a decisive factor governing the DA reaction kinetics.…”

Section: Introductionmentioning

confidence: 99%

Understanding the intermolecular Diels–Alder cycloaddition promotion: Activation strain model/energy decomposition analysis model and conceptual density functional theory viewpoints

et al. 2021

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The present work reports the computational study of the major Diels-Alder reaction between 2-bromocycloalkenone and a variety of mono-and di-substituted dienes.Through density functional theory (DFT) calculations and subsequent activation strain model/energy decomposition analysis/conceptual DFT (C-DFT) analyses, the key factors governing the activation barriers heights, and thus reactivity, are characterized. In contrast with a previous study, steric effects do not appear to control reactivity. Conversely, in all presented cases, a subtle interplay between deformation and interaction energies is evidenced at transition states. In the end, neither term alone is enough to explain or predict reactivity. Yet a simple C-DFT descriptor allows to predict with a reasonable efficiency the activation barriers: the excitation energy needed to observe a charge transfer from the diene to the dienophile. Theoretical elements are provided to support the use of this descriptor.

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Computational Studies of the Reactivity, Regio-Selectivity and Stereo-Selectivity of Pericyclic Diels-Alder Reactions of Substituted Cyclobutenones

Cited by 5 publications

References 29 publications

Theoretical Investigation of Steric Effect Influence on Reactivity of Substituted Butadienes with Bromocyclobutenone

Theoretical Investigation of Steric Effect Influence on Reactivity of Substituted Butadienes with Bromocyclobutenone

Synthesis of β‐Substituted meso‐Tetraaryl‐21,23‐dithiaporphyrins by Heck Reaction

Understanding the intermolecular Diels–Alder cycloaddition promotion: Activation strain model/energy decomposition analysis model and conceptual density functional theory viewpoints

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