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A DFT mechanistic study on oxidative dehydrogenative Diels–Alder reaction of alkylbenzenes
Journal of Molecular Graphics and Modelling ( IF 2.9 ) Pub Date : 2021-01-14 , DOI: 10.1016/j.jmgm.2021.107839
Ahmed Yusif Abdulai 1 , Richard Tia 1 , Evans Adei 1
Affiliation  

Cross-dehydrogenative Diels-Alder cycloaddition reaction between readily-available alkyl benzenes and electron-deficient dienophiles is an attractive synthetic route to access carbocyclic compounds which have high utility in the chemical and pharmaceutical industries. This work reports a study at the M06-2X/6-311G(d) and M06-2X/6–311++G(d,p) levels of theory on the reaction of alkyl benzenes with electron-deficient dienophiles in the presence of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an oxidant and hydroquinone as an activator, so as to understand the chemoselectivity of the reaction (addition across the alkene functionality versus the ketone functionality), the role of the activator, the effects of substituents and the effect of solvent on the reaction. The results show the addition of the alkene bonds of methylstyrene across the alkene functionality of the electron-deficient dienophiles has generally low barriers compared to the addition across the carbonyl functionality of the electron-deficient dienophile. Powerful electron-withdrawing group (cyano) on the electron-deficient dienophile decrease the energy barrier for the cycloaddition and decrease the stability of the product whiles weak electron-withdrawing (bromine and chlorine) and electron-donating groups increase the energy barrier for the cycloaddition and decrease the stability of the product. The hydroquinone as an activator decreases the activation barrier for the Diels-Alder cycloaddition reaction.



中文翻译:

烷基苯氧化脱氢Diels-Alder反应的DFT机理研究

易于获得的烷基苯与缺电子的亲二烯体之间的交叉脱氢Diels-Alder环加成反应是一种吸引人的合成途径,可用于在化学和制药工业中具有较高效用的碳环化合物。这项工作报告了在存在条件下烷基苯与缺电子的亲二烯体反应的M06-2X / 6-311G(d)和M06-2X / 6-311 ++ G(d,p)理论水平的研究2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)作为氧化剂和对苯二酚作为活化剂,以了解反应的化学选择性(烯烃功能上的加成与酮功能上的加成) ,活化剂的作用,取代基的作用以及溶剂对反应的影响。结果表明,与缺乏电子的亲二烯体的羰基官能团相比,在缺乏电子的亲二烯体的烯烃官能团间添加甲基苯乙烯的烯键通常具有较低的势垒。缺电子的亲二烯体上的强大的吸电子基团(氰基)降低了环加成的能垒,降低了产品的稳定性,而弱的吸电子基团(溴和氯)和给电子基团增加了环加成的能垒并降低产品的稳定性。对苯二酚作为活化剂降低了Diels-Alder环加成反应的活化障碍。

更新日期:2021-02-01
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