小柯机器人

Creating High Regioselectivity by Electronic Metal–Support Interaction of a Single-Atomic-Site Catalyst
2021-09-14 15:29

清华大学王定胜团队通过单原子位点催化剂的金属-载体相互作用产生高区域选择性。相关研究成果发表在2021年9月10日出版的国际学术期刊《美国化学会杂志》。

配体是控制有机反应区域选择性最常用的手段。开发新的区域选择性控制方法对有机合成具有重要意义。

在该研究中,研究人员通过研究各种反应机理,设计并合成了具有强电子金属-载体相互作用(EMSI)效应的单原子位催化剂(SAC),即Cu1-TiC。利用瞬态富电子特性,在反应过程中,金属催化中间体上炔烃的π云回馈增强。通过该方式,该反应实现了电子无偏炔烃的高度线性E型区域选择性转化,并完全避免了支链异构体的形成(ln:br>100:1,TON高达612,比先前记录的高3倍)。

SACs的结构元件按照合成机理的要求进行设计。催化剂中的每一种元素在合成机理中都起着重要作用。这表明,通常被认为是提高多相催化中催化效率和持久性的EMSI,首次显示出调节均相催化中区域选择性的令人兴奋的潜力。

附:英文原文

Title: Creating High Regioselectivity by Electronic Metal–Support Interaction of a Single-Atomic-Site Catalyst

Author: Wen-Hao Li, Jiarui Yang, Hongyu Jing, Jian Zhang, Yu Wang, Jiong Li, Jie Zhao, Dingsheng Wang, Yadong Li

Issue&Volume: September 10, 2021

Abstract: 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. π 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.

DOI: 10.1021/jacs.1c08088

Source: https://pubs.acs.org/doi/10.1021/jacs.1c08088

 

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