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首页> 外文期刊>Chemistry: A European journal >Electronic Control on Linear versus Branched Alkylation of 2-/3-Aroylbenzofurans with Acrylates: Combined DFT and Synthetic Studies
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Electronic Control on Linear versus Branched Alkylation of 2-/3-Aroylbenzofurans with Acrylates: Combined DFT and Synthetic Studies

机译：用丙烯酸酯的2- / 3-芳酰苯并呋喃的线性电子控制与2- / 3-芳酰苯甲苯脲的分支烷基化：联合DFT和合成研究

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摘要

Investigations on the factors that govern unusual branched alkylation of 2-aroylbenzofurans with acrylates by Ru-catalyzed carbonyl-directed C-H activation has been carried out by calculating the kinetics associated with the two key steps—the coordination of the acrylate with the intermediate ruthenacycle and the subsequent migratory insertion reaction—studied with the help of DFT calculations. Eight possible orientations for each mode of alkylation have been considered for the calculations. From these calculations, it has been understood that there is a synergistic operation of the steric and electronic effects favoring the branched alkylation. Further DFT investigations on the alkylation of the isomeric 3-aroylbenzofurans indicated a preference for the linear alkylation and this has been verified experimentally. Overall, the observed/calculated complementary selectivity in the alkylation of 2-/3-aroylbenzofurans with acrylates reveals that the substrate-dependent charge distribution of the Ru-C bond in the intermediate ruthenacycle is an important determining factor and thus the current work opens up a new domain of substrate design for controlling regioselectivity.
机译：通过计算与双关键步骤相关的动力学 - 通过计算与两个关键步骤相关的动力学来进行丙烯酸酯的丙烯酸酯的丙烯酸酯的丙烯酸酯的异常支链烷基化的因素研究 - 用中间钌循环的丙烯酸酯的协调随后的迁移插入反应 - 在DFT计算的帮助下研究。已经考虑了每种烷基化模式的八种可能的取向来进行计算。从这些计算中，已经理解，存在有利于支链烷基化的空间和电子效应的协同操作。进一步的DFT研究对异构3-芳酰苯甲苯脲烷基化的烷基化表明了对线性烷基化的偏好，并且这已经通过实验验证。总体而言，使用丙烯酸酯的2- / 3-芳酰苯甲苄异福坦的烷基化的观察/计算的互补选择性显示，中间钌谱系中Ru-C键的基材依赖性电荷分布是一个重要的决定因素，因此目前的工作开放一种用于控制区域选择性的基板设计的新域。

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