Benz Sebastian, Mareda Jiri, Besnard Céline, Sakai Naomi, Matile Stefan
Department of Organic Chemistry , University of Geneva , Geneva , Switzerland .
Chem Sci. 2017 Dec 1;8(12):8164-8169. doi: 10.1039/c7sc03866f. Epub 2017 Oct 16.
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 σ 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 -xylene, crystal structure, σ 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 σ holes down to = 11 μM in THF. Catalytic activities follow the same trend and culminate in rate enhancements for transfer hydrogenation of quinolines beyond 100 000.
本报告中介绍的苯并二硒唑（BDS）首次满足了在中性骨架中强硒供体上构象固定的σ空穴焦点处进行非共价高精度硫族元素键催化的所有先决条件。对长Se-C键进行合理的咬角调整是BDS设计的关键。对于前所未有的BDS基序，报道了从对二甲苯合成12种类似物、晶体结构、σ空穴变化策略、光电性质、理论和实验阴离子结合以及催化活性。在四氢呋喃中，氯离子结合随着σ空穴深度的增加而增加，最低可达11 μM。催化活性遵循相同的趋势，喹啉转移氢化的速率增强最终超过100000。
