Phosphine-Built-In Porous Organic Cage Supported Ultrafine Pd Nanoclusters Enable Highly Efficient and Regioselective Hydrogenation of Epoxides  

作　　者：Xin Zhou Zhaozhan Wang Zhe-Ning Chen Yong Yang 

机构地区：[1]CAS Key Laboratory of Bio-Based Materials,Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266101 [2]Shandong Energy Institute,Qingdao 266101 [3]College of Environment and Safety Engineering,Qingdao University of Science and Technology,Qingdao 266101 [4]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002 [5]University of Chinese Academy of Sciences,Beijing 100049 [6]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry,Xiamen University,Xiamen 361005

出　　处：《CCS Chemistry》2024年第10期2476-2488,共13页中国化学会会刊（英文）

基　　金：the National Natural Science Foundation of China(grant nos.22078350 and 22308368);the Shandong Province Key Research and Development Plan(grant no.2023CXG010607);the Natural Science Foundation of Shandong Province(grant nos.ZR2020KB016 and ZR2022QB026).

摘　　要：Selective hydrogenation of epoxides has been regarded as an atom-economical and straightforward method for the synthesis of alcohols.However,it remains a big challenge in the precise control of regioselectivity.To date,the reaction enabled by a reusable and high-performance heterogeneous catalyst with excellent regioselectivity is very scarce.Herein,we develop highly loaded and ultrafine Pd nanoclusters(NCs)encapsulated on a phosphinebuilt-in porous organic cage(FPPOC)for the catalytic hydrogenation of epoxides by molecular hydrogen.Benefiting from the unique characters of uniform dispersion and strong interaction between Pd NCs and FPPOC,the resultant Pd NCs exhibited superior catalytic activity and excellent regioselectivity for the hydrogenation of epoxides under milder conditions.A diverse set of terminal and internal epoxides was efficiently reduced to the corresponding linear or branched alcohols in an extremely regioselective manner,well tolerating diverse functional groups.Remarkably,the catalyst demonstrates high stability and could be reused up to 10 times with marginal decay in activity and regioselectivity.Furthermore,the catalyst is applicable for scale-up synthesis with a record turnover number as high as 16,111,to the best of our knowledge,outperforming those previous state-of-the-art catalysts.Control experiments and characterizations in combination with density functional theory calculations provide insight into the superior activity and excellent regioselectivity.

关 键 词：porous organic cage phosphine-built-in palladium nanoclusters regioselective hydrogenation EPOXIDES 

分 类 号：O64[理学—物理化学]