Molecular recognition-based catalysis in nucleophilic aromatic substitution: a mechanistic study
Molecular recognition-based catalysis in nucleophilic aromatic substitution: a mechanistic study
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DOI：
10.1039/c2nj40128b
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发表时间：
2012-01-01
影响因子：
3.3
通讯作者：
Perez-Lorenzo, Moises
中科院分区：
文献类型：
--
作者：
Basilio, Nuno;Garcia-Rio, Luis;Perez-Lorenzo, Moises
在糖基和冠醚的存在下，硝基活化底物的亲核芳香取代被报道。动力学研究揭示了聚醚催化SNAr反应机理的多面性，以及影响反应过程的主要特征。因此，该过程可以通过分子识别过程由催化剂有效地控制，也强烈依赖于底物的电子结构，因此，产生了一个通用的反应系统。本文提出的动力学模型可以量化通过不同途径进行的反应的分数。关于催化剂和底物之间主客体相互作用性质的信息也将被提取出来。
Nucleophilic aromatic substitution for nitro-activated substrates in the presence of glymes and crown ethers is reported. The kinetic study reveals the many-sided nature of the polyether-catalyzed SNAr mechanism as well as the main features affecting the course of the reaction. Thus, the process can be efficiently controlled by the catalyst through a molecular-recognition process, being also strongly dependent on the electronic structure of the substrate and, therefore, giving rise to a versatile reaction system. The kinetic model proposed herein allows quantifying the fractions of reaction proceeding through the different routes. Information on the nature of the host-guest interaction between the catalyst and the substrate will also be extracted.