文献类型：期刊文献

英文题名：Creating High Regioselectivity by Electronic Metal-Support Interaction of a Single-Atomic-Site Catalyst

作者：Li, Wen-Hao[1];Yang, Jiarui[1];Jing, Hongyu[1];Zhang, Jian[1];Wang, Yu[2];Li, Jiong[2];Zhao, Jie[3];Wang, Dingsheng[1];Li, Yadong[1]

机构：[1]Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China;[2]Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2021

卷号：143

期号：37

起止页码：15453

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20213910957686);WOS:【SCI-EXPANDED(收录号:WOS:000700883200058)，CCR-EXPANDED(收录号:WOS:000700883200058)】；

基金：This work was supported by the National Key R&D Program of China (2018YFA0702003), the National Natural Science Foundation of China (21890383, 21871159), Science and Technology Key Project of Guangdong Province of China (2020B010188002), and Beijing Municipal Science & Technology Commission (No. Z191100007219003).

语种：英文

外文关键词：Catalysis - Hydrocarbons - Catalysts - Reaction intermediates - Isomers

摘要：Ligands are the most commonly used means to control the regioselectivity of organic reactions. It is very important to develop new regioselective control methods for organic synthesis. In this study, we designed and synthesized a single-atomic-site catalyst (SAC), namely, Cu1-TiC, with strong electronic metal-support interaction (EMSI) effects by studying various reaction mechanisms. pi cloud back-donation to the alkyne on the metal catalytic intermediate was enhanced during the reaction by using transient electron-rich characteristics. In this way, the reaction achieved highly linear-E-type regioselective conversion of electronically unbiased alkynes and completely avoided the formation of branched isomers (ln:br >100:1, TON up to 612, 3 times higher than previously recorded). The structural elements of the SACs were designed following the requirements of the synthesis mechanism. Every element in the catalyst played an important role in the synthesis mechanism. This demonstrated that the EMSI, which is normally thought to be responsible for the improvement in catalytic efficiency and durability in heterogeneous catalysis, now first shows exciting potential for regulating the regioselectivity in homogeneous catalysis.