Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder <i>endo</i>:<i>exo</i> Selectivity

Larrañaga, Olatz; Cózar, Abel de

doi:10.1002/open.201800237

Cited by 8 publications

(3 citation statements)

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“…The ASM can be applied to all unimolecular and bimolecular reactions in both homogeneous and heterogeneous systems and has been used routinely by theoretical and experimental chemists [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] . We provide specific examples of the ASM being applied to understand inorganic, organic, and supramolecular chemistries, namely, the transition metal-mediated oxidative addition of C-X bonds in cross-coupling reactions, the reactivity of cycloalkynes in 1,3-dipolar cycloadditions, the reactivity of dihalogen-catalyzed Michael addition reactions, and the bonding mechanism in hydrogen-bonded systems.…”

Section: Applications Of the Methodsmentioning

confidence: 99%

Understanding chemical reactivity using the activation strain model

et al. 2020

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Section: Applications Of the Methodsmentioning

confidence: 99%

Understanding chemical reactivity using the activation strain model

et al. 2020

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“…Preparation of structures for the ASM analysis along the IRC was carried out with the help of the autoDIAS program by Svatunek and Houk . The ASM analyses have been successfully used for the understanding of chemical reactions in the field of organic − and organometallic chemistry − and more recently in heterogeneous catalysis …”

Section: Theory and Computational Detailsmentioning

confidence: 99%

Rationalizing the Substituent Effects in Diels–Alder Reactions of Triazolinediones with Anthracene

2022

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In this work we tackle the problem of the substituent effects in the Diels–Alder cycloadditions between triazolinediones (TADs) and anthracene. Experiments showed that aryl TADs substituted with electron-withdrawing groups (EWG) are more reactive than those substituted with electron-donating (EDG) or alkyl groups. However, the molecular origin of this preference is not yet understood. By a combination of methods including the activation strain model (ASM), energy decomposition analysis (EDA), molecular orbital (MO) theory, and conceptual density functional theory (CDFT), we disclosed the substituent effects of TADs. First, ASM/EDA analysis revealed that the reactivity of alkyl and aryl-substituted TADs is controlled by interaction energies, ΔE int, which are ultimately defined by orbital interactions between frontier molecular orbitals. Moreover, alkyl-TADs are also controlled by the extent of strain at the transition state. The MO analysis suggested that the rate acceleration for EWG-substituted TADs is due to a more favorable orbital interaction between the HOMO of anthracene and the LUMO of the TADs, which is corroborated by calculations of charge transfer at the transition states. From CDFT, the chemical potential of anthracene is higher than those of TADs, indicating a flow of electron density from anthracene to TADs, in agreement with the results from the electrophilicity index.

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“…Note that for such a reaction a very small difference between the two stereomers is expected. 38 Finally, at 1 atm the pre-TS has an energy lying in between the reactants and the TS, as in the IRC calculations from which the structures were extracted.…”

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confidence: 99%