The origin of selectivity in the trimerization of 1,3-cyclopentadiene from an activation strain perspective

IF 2.1 4区 化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY Journal of Molecular Modeling Pub Date : 2024-09-03 DOI:10.1007/s00894-024-06117-6
Ravshan S. Shamsiev, Nikolai A. Dontsenko
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Abstract

Context

Quantum chemical modeling (DFT-PBE0/cc-pVTZ) of the [4 + 2]-cycloaddition reaction of 1,3-cyclopentadiene (CPD) to (exo/endo)-dicyclopentadiene (DCPD) was carried out, resulting in 14 products—CPD trimers. According to calculations, exo-addition of CPD to the norbornene (NB) fragment of DCPD and trans-addition of CPD to the cyclopentene (CP) fragment of DCPD are kinetically preferred. Ring strain energies ERS were calculated for all trimers using the homodesmotic reaction approach. The least strained trimers are formed by exo-addition of CPD to the NB fragment of exo-DCPD, while the most strained ones are formed by endo-addition of CPD to the NB fragment of endo-DCPD. ERS values are in good agreement with thermodynamic stability of trimers. Analysis of activation energy using the activation strain model showed steric effects causing deformation of the DCPD molecule upon reaching the transition state to be the leading factor of the magnitude of the cycloaddition reaction activation barrier. Deformation of the DCPD molecule mostly occurs in two dihedral angles—the angle of escape of H atoms from the plane of the double bond involved in cycloaddition and the angle between the NB and CP fragments. The sum of deviations of these angles in the transition states (or products) structures is in good agreement with Gibbs activation energies of cycloaddition reactions of CPD to DCPD.

Methods

Quantum chemical calculations were carried out using density functional theory in Gaussian 09 software. Hybrid exchange–correlation PBE0 functional was used with cc-pVTZ basis set.

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从活化应变的角度看 1,3-环戊二烯三聚反应选择性的起源。
背景:对 1,3-环戊二烯(CPD)与(外/内)-双环戊二烯(DCPD)的[4 + 2]-环加成反应进行了量子化学建模(DFT-PBE0/cc-pVTZ),得到了 14 种产物-CPD 三聚体。根据计算,CPD 与二环戊二烯的降冰片烯(NB)片段的外向加成和 CPD 与二环戊二烯的环戊烯(CP)片段的反向加成在动力学上是优先的。采用同质反应法计算了所有三聚体的环应变能 ERS。应变最小的三聚体是 CPD 与外-DCPD 的 NB 片段外加形成的,而应变最大的三聚体是 CPD 与内-DCPD 的 NB 片段内加形成的。ERS 值与三聚体的热力学稳定性十分吻合。使用活化应变模型对活化能进行的分析表明,立体效应导致 DCPD 分子在达到过渡态时发生形变,这是环化反应活化障碍大小的主要因素。DCPD 分子的变形主要发生在两个二面角上--H 原子从参与环化反应的双键平面上逃逸的角度以及 NB 和 CP 片段之间的角度。这些角度在过渡态(或产物)结构中的偏差总和与 CPD 与 DCPD 环化反应的吉布斯活化能十分吻合:方法:使用高斯 09 软件中的密度泛函理论进行量子化学计算。采用混合交换相关 PBE0 函数和 cc-pVTZ 基集。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Journal of Molecular Modeling
Journal of Molecular Modeling 化学-化学综合
CiteScore
3.50
自引率
4.50%
发文量
362
审稿时长
2.9 months
期刊介绍: The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling. Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry. Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.
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