Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study

IF 1.1 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Heteroatom Chemistry Pub Date : 2020-09-18 DOI:10.1155/2020/8885991

S. E. Hamidi, M. Khnifira, E. M. Lemdek, R. Hammal, Noureddine Barka, M. Sadiq, A. Benharref, A. Chekroun, H. Zgou, M. Abdennouri

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引用次数: 2

Abstract

This study was performed to understand the site selectivity in the reaction between β-himachalene and meta-chloroperbenzoic acid (m-CPBA) in the first step followed by the addition of dibromocarbene (CBr2) to the main monoepoxidation product Pα formed in the first reaction. Calculations were performed using the Becke three-parameter hybrid exchange functional and the Lee–Yang–Parr correlation functional (B3LYP) with the 6-311 + G (d, p) basis set. Transition states were located by QST2, and their highlighting was validated by the existence of only one imaginary frequency in the Hessian matrix. The action of m-CPBA on β-himachalene was analyzed on the two double bonds of β-himachalene whose theoretical calculations show that the attack affects the most substituted double bond on α side containing hydrogen of ring junction. The obtained Pα product thereafter treated with dibromocarbene leads via an exothermic reaction to the six-membered ring double bond position of α-monoepoxide. The major products Pαα are kinetically and thermodynamically favored with a high stereoselectivity in perfect correlation with the experimental observations.

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间氯过苯甲酸与二溴卡宾与β-喜马偕烯反应的机理及选择性研究

本研究旨在了解β-himachalene与间氯过苯甲酸（m-CPBA）在第一步反应中的位点选择性，然后将二溴卡宾（CBr2）加入到第一步反应形成的主要单环氧化产物Pα中。使用Becke三参数混合交换泛函和Lee–Yang–Parr相关泛函（B3LYP）进行计算，6-311 + G（d，p）基集。通过QST2定位过渡态，并通过Hessian矩阵中仅存在一个虚频率来验证它们的突出显示。从β-himachalene的两个双键上分析了m-CPBA对β-himchalene的作用，理论计算表明，该攻击影响了环结含氢α侧最取代的双键。然后用二溴卡宾处理得到的Pα产物通过放热反应到达α-单环氧化物的六元环双键位置。主要产物Pαα在动力学和热力学上是有利的，具有高的立体选择性，与实验观察结果完全相关。

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

Heteroatom Chemistry 化学-化学综合

CiteScore

1.20

自引率

0.00%

发文量

审稿时长

6 months

期刊介绍： Heteroatom Chemistry brings together a broad, interdisciplinary group of chemists who work with compounds containing main-group elements of groups 13 through 17 of the Periodic Table, and certain other related elements. The fundamental reactivity under investigation should, in all cases, be concentrated about the heteroatoms. It does not matter whether the compounds being studied are acyclic or cyclic; saturated or unsaturated; monomeric, polymeric or solid state in nature; inorganic, organic, or naturally occurring, so long as the heteroatom is playing an essential role. Computational, experimental, and combined studies are equally welcome. Subject areas include (but are by no means limited to): -Reactivity about heteroatoms for accessing new products or synthetic pathways -Unusual valency main-group element compounds and their properties -Highly strained (e.g. bridged) main-group element compounds and their properties -Photochemical or thermal cleavage of heteroatom bonds and the resulting reactivity -Uncommon and structurally interesting heteroatom-containing species (including those containing multiple bonds and catenation) -Stereochemistry of compounds due to the presence of heteroatoms -Neighboring group effects of heteroatoms on the properties of compounds -Main-group element compounds as analogues of transition metal compounds -Variations and new results from established and named reactions (including Wittig, Kabachnik–Fields, Pudovik, Arbuzov, Hirao, and Mitsunobu) -Catalysis and green syntheses enabled by heteroatoms and their chemistry -Applications of compounds where the heteroatom plays a critical role. In addition to original research articles on heteroatom chemistry, the journal welcomes focused review articles that examine the state of the art, identify emerging trends, and suggest future directions for developing fields.