Catalysis with chalcogen bonds: neutral benzodiselenazole scaffolds with high-precision selenium donors of variable strength
Catalysis with chalcogen bonds: neutral benzodiselenazole scaffolds with high-precision selenium donors of variable strength
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DOI：
10.1039/c7sc03866f
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发表时间：
2017-12-01
期刊：
影响因子：
8.4
通讯作者：
Matile, Stefan
中科院分区：
文献类型：
--
作者：
Benz, Sebastian;Mareda, Jiri;Matile, Stefan
在本报告中介绍的苯并二硒唑（BDS）的履行，第一次，所有的先决条件，非共价高精度硫族元素键合催化的焦点构象固定的σ孔强硒供体在中性支架。合理调整长Se-C键的咬合角是BDS设计的关键。对于前所未有的BDS基序，合成12个类似物从邻二甲苯，晶体结构，σ孔变化策略，光电性能，理论和实验的阴离子结合以及催化活性的报告。氯离子结合的增加与深度的s孔下降到K-D = 11 μ M在THF中。催化活性遵循相同的趋势，并最终在喹啉的转移氢化超过100 000的速率增强。
The benzodiselenazoles (BDS) introduced in this report fulfill, for the first time, all the prerequisites for non-covalent high-precision chalcogen-bonding catalysis in the focal point of conformationally immobilized sigma holes on strong selenium donors in a neutral scaffold. Rational bite-angle adjustment to the long Se-C bonds was the key for BDS design. For the unprecedented BDS motif, synthesis of 12 analogs from o-xylene, crystal structure, sigma hole variation strategies, optoelectronic properties, theoretical and experimental anion binding as well as catalytic activity are reported. Chloride binding increases with the depth of the s holes down to K-D = 11 mu M in THF. Catalytic activities follow the same trend and culminate in rate enhancements for transfer hydrogenation of quinolines beyond 100 000.