温控配体与液/液两相催化

Liquid/Liquid Two Phase Catalysis Based on Thermoregulated Ligands

以作者近年的研究工作为主 ,对液 /液两相催化研究领域取得的进展做一综述 .着重介绍了以温控配体为基础的新型液 /液两相催化过程温控相转移催化 (thermoregulatedphasetransfercatalysis ,TRPTC)和温控相分离催化 (thermoregulatedphase separablecatalysis,TPSC)的基本原理及其在高碳烯烃氢甲酰化、芳香硝基化合物的CO选择性还原及烯烃加氢等反应中的应用 .基于温控配体在水中的“浊点”特性而提出的温控相转移催化概念 ,为从根本上解决水 /有机两相催化的适用范围受底物水溶性限制的问题提供了一条新途径 .而利用温控配体在某些有机溶剂中存在临界溶解温度 (CST)的特性而实现的温控相分离催化 ,则使在高于临界溶解温度的反应温度时为均相的反应体系 ,在低温 (<CST)时则分成两相 ,催化剂自成一相 ,形成一种具有“均相反应、两相分离”特色的液

Our research results and recent developments of biphasic catalysis are surveyed. Emphasis is put on the general principles of thermoregulated phase transfer catalysis (TRPTC) and thermoregulated phase separable catalysis (TPSC), based on thermoregulated ligands, and on their applications in hydroformylation of higher olefins, CO selective reduction of nitroarenes, and hydrogenation of olefins. The conception of TRPTC is proposed based on the cloud point of thermoregulated ligands. It is an improvement of the classical biphasic catalysis, whose applications are restrained by the water solubility of organic substrates. Additionally, based on the critical solution temperature (CST) of thermoregulated ligands in certain organic solvents, a novel biphasic catalysis system named as thermoregulated phase separable catalysis is proposed. That is, when reaction temperature is higher than the CST, the whole system is homogeneous; after reaction, when cooled to a room temperature lower than the CST, the system separates into two phases, in which the catalyst precipitates from the organic phase and retains into a single phase. TPSC is characterized by homogeneous catalysis coupled with convenient biphasic separation. It is a new system of liquid/liquid two phase catalysis.