Hou Sheng-Li, Dong Jie, Jiang Xiao-Lei, Jiao Zhuo-Hao, Zhao Bin
College of Chemistry, Key Laboratory of Advanced Energy Material Chemistry, MOE, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300071, China.
Angew Chem Int Ed Engl. 2019 Jan 8;58(2):577-581. doi: 10.1002/anie.201811506. Epub 2018 Dec 5.
Cyclization of propargylic alcohols with CO is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between Cu and In plays a key role in the conversion of CO .
炔丙醇与一氧化碳的环化反应是工业上的一个重要反应,通常使用贵金属催化剂以确保在环境友好的条件下获得高产品收率。在此,合成了一种具有直径为1.66 nm的大一维通道的无贵金属多孔骨架1用于该反应。化合物1表现出优异的酸碱稳定性,甚至在腐蚀性的三乙胺中稳定一个月。催化研究表明,1是炔丙醇与一氧化碳在温和条件下无需任何溶剂进行环化反应的有效催化剂,其周转数(TON)可达创纪录的14400。此外,当使用生物大分子炔诺酮作为底物时,这种金属有机框架催化剂也具有罕见的催化活性。机理研究表明,铜和铟之间的协同催化作用在一氧化碳的转化中起关键作用。