Improved synthesis of symmetrically & asymmetrically N-substituted pyridinophane derivatives.
Improved synthesis of symmetrically & asymmetrically N-substituted pyridinophane derivatives.
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改进的对称合成
DOI：
10.1039/c7ob02508d
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发表时间：
2017
影响因子：
3.2
通讯作者：
Mirica,LiviuM
中科院分区：
文献类型：
--
作者：
Wessel,AndrewJ;Schultz,JasonW;Tang,Fengzhi;Duan,Hui;Mirica,LiviuM
N，N′-二（甲苯磺酰基）-2，11-二氮杂[3，3]（2，6）吡啶并噻吩（TsN 4）前体被用作制备各种对称和不对称吡啶并噻吩衍生配体的起始点。已经发表了各种合成TsN 4的方法，但关键的问题是从较大的18元和24元氮杂大环中纯化TsN 4。最常见的是，柱色谱法或其他费力的方法已被用于这种分离，但我们已经发现了一种替代的选择性溶解方法后，质子化，允许多克规模的输出TsN 4·HCl。TsN 4的这种优化合成也导致了对称RN 4衍生物以及不对称衍生物N-（甲苯磺酰基）-2，11-二氮杂[3，3]（2，6）吡啶并吡喃（TsHN 4）的开发。使用这种TsHN 4前体，可以添加不同的N-取代基以产生不对称RR′N4大环配体库。这些不对称的RR′N4衍生物扩展了RN 4骨架在配位化学中的应用，以及研究这些吡啶并噻吩配体对金属中心的电子、空间和齿位效应的能力。
The N,N′-di(toluenesulfonyl)-2,11-diaza[3,3](2,6)pyridinophane (TsN4) precursor was sought after as a starting point for the preparation of various symmetric and asymmetric pyridinophane-derived ligands. Various procedures to synthesize TsN4 had been published, but the crucial problem had been the purification of TsN4 from the larger 18- and 24-membered azamacrocycles. Most commonly, column chromatography or other laborious methods have been utilized for this separation, yet we have found an alternate selective dissolution method upon protonation which allows for multi-gram scale output of TsN4·HCl. This optimized synthesis of TsN4 also led to the development of symmetric RN4 derivatives as well as the asymmetric derivative N-(tosyl)-2,11-diaza[3,3](2,6)pyridinophane (TsHN4). Using this TsHN4 precursor, different N-substituents can be added to create a library of asymmetric RR′N4 macrocyclic ligands. These asymmetric RR′N4 derivatives expand the utility of the RN4 framework in coordination chemistry and the ability to study the electronic, steric, and denticity effects of these pyridinophane ligands on the metal center.