Systematic Variation of Ligand and Cation Parameters Enables Site-Selective C-C and C-N Cross-Coupling of Multiply Chlorinated Arenes through Substrate-Ligand Electrostatic Interactions
Systematic Variation of Ligand and Cation Parameters Enables Site-Selective C-C and C-N Cross-Coupling of Multiply Chlorinated Arenes through Substrate-Ligand Electrostatic Interactions
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DOI：
10.1021/jacs.0c11056
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发表时间：
2020-12-30
影响因子：
15
通讯作者：
Phipps, Robert J.
中科院分区：
文献类型：
--
作者：
Golding, William A.;Schmitt, Hendrik L.;Phipps, Robert J.
使用有吸引力的配体和底物之间的非共价相互作用是一个新兴的战略控制位置的选择性。一个关键的问题涉及是否精细控制的分子与多个，紧密间隔的反应位置是可以实现的使用通常较少的方向性静电相互作用。在此，我们应用10件“工具包”，包括两个密切相关的磺化膦配体和五个基地，每个拥有不同的阳离子大小，多氯芳烃的位点选择性交叉偶联的挑战。这些配体/碱组合提供的微调是有效的Suzuki-Miyaura耦合和Buchwald-Hartwig耦合的异构体二氯化和三氯化芳烃的范围内，基板，将产生棘手的混合物时，使用典型的配体。本研究为位点选择性交叉偶联生成复杂的高取代芳烃提供了一种实用的解决方案。
Use of attractive noncovalent interactions between ligand and substrate is an emerging strategy for controlling positional selectivity. A key question relates to whether fine control on molecules with multiple, closely spaced reactive positions is achievable using typically less directional electrostatic interactions. Herein, we apply a 10-piece "toolkit" comprising of two closely related sulfonated phosphine ligands and five bases, each possessing varying cation size, to the challenge of site-selective cross-coupling of multiply chlorinated arenes. The fine tuning provided by these ligand/base combinations is effective for Suzuki-Miyaura coupling and Buchwald-Hartwig coupling on a range of isomeric dichlorinated and trichlorinated arenes, substrates that would produce intractable mixtures when typical ligands are used. This study develops a practical solution for site-selective cross-coupling to generate complex, highly substituted arenes.