Zhang Yao-Yao, Yang Guan-Wen, Xie Rui, Yang Li, Li Bo, Wu Guang-Peng
MOE Laboratory of Macromolecular Synthesis and Functionalization, Adsorption and Separation Materials and Technologies of Zhejiang Province, Department of Polymer Science and Engineering, Zhejiang University, Zhe Da Road 38, Hangzhou, 310027, China.
College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Yuhangtang Road 2318, Hangzhou, 311121, China.
Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23291-23298. doi: 10.1002/anie.202010651. Epub 2020 Oct 15.
A series of highly active organoboron catalysts for the coupling of CO and epoxides with the advantages of scalable preparation, thermostability, and recyclability is reported. The metal-free catalysts show high reactivity towards a wide scope of cyclic carbonates (14 examples) and can withstand a high temperature up to 150 °C. Compared with the current metal-free catalytic systems that use mol % catalyst loading, the catalytic capacity of the catalyst described herein can be enhanced by three orders of magnitude (epoxide/cat.=200 000/1, mole ratio) in the presence of a cocatalyst. This feature greatly narrows the gap between metal-free catalysts and state-of-the-art metallic systems. An intramolecular cooperative mechanism is proposed and certified on the basis of investigations on crystal structures, structure-performance relationships, kinetic studies, and key reaction intermediates.
报道了一系列用于CO与环氧化合物偶联的高活性有机硼催化剂，这些催化剂具有可规模化制备、热稳定性和可回收性的优点。这些无金属催化剂对多种环状碳酸酯显示出高反应活性（14个实例），并且能够承受高达150 °C的高温。与目前使用摩尔百分比催化剂负载量的无金属催化体系相比，在助催化剂存在下，本文所述催化剂的催化能力可提高三个数量级（环氧化物/催化剂 = 200 000/1，摩尔比）。这一特性极大地缩小了无金属催化剂与最先进金属体系之间的差距。在对晶体结构、结构-性能关系、动力学研究和关键反应中间体进行研究的基础上，提出并证实了一种分子内协同机制。
