Li Wen-Hao, Li Cun-Yao, Xiong Huan-Yan, Liu Yang, Huang Wen-Yong, Ji Guang-Jun, Jiang Zheng, Tang Hai-Tao, Pan Ying-Ming, Ding Yun-Jie
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin, 541004, China.
Dalian National Laboratory for Clean Energy, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Angew Chem Int Ed Engl. 2019 Feb 18;58(8):2448-2453. doi: 10.1002/anie.201814493. Epub 2019 Jan 24.
Heterogeneous, metal, single-site catalysts often exhibit higher catalytic performance than other catalysts because of their maximized atom efficiency of 100 %. Reported herein is a precoordination/solvothermal polymerization strategy to fabricate a stable mononuclear Pd-metalized porous organic polymer catalyst (Pd@POP). Pd@POP was easy to use in regioselective organic reactions because the internal structure of this Pd@POP can be easily modified. The catalyst was used to solve the intractable regioselectivity problems of Heck reactions. Pd@POP-9 can efficiently activate the ends of olefins, thereby leading to high selectivity for substitution at the external position. To understand the reason underlying the high selectivity and activity of the catalyst, the systemic characterization of Pd@POP-9 and density-functional theory calculations were conducted. This Heck reaction is the first to be catalyzed by a recyclable mononuclear metal catalyst with unprecedented catalytic activity and regioselectivity.
多相、金属、单中心催化剂由于其100%的原子效率最大化，通常表现出比其他催化剂更高的催化性能。本文报道了一种预配位/溶剂热聚合策略，用于制备稳定的单核钯金属化多孔有机聚合物催化剂（Pd@POP）。Pd@POP易于用于区域选择性有机反应，因为这种Pd@POP的内部结构可以很容易地进行修饰。该催化剂用于解决Heck反应棘手的区域选择性问题。Pd@POP-9能够有效活化烯烃末端，从而对外位取代产生高选择性。为了理解该催化剂高选择性和活性的原因，对Pd@POP-9进行了系统表征并进行了密度泛函理论计算。该Heck反应首次由可回收的单核金属催化剂催化，具有前所未有的催化活性和区域选择性。
