文献类型：期刊文献

英文题名：Unleash electron transfer in C-H functionalization by mesoporous carbon-supported palladium interstitial catalysts

作者：Zhao, Xiaorui[1];Cao, Yueqiang[2];Duan, Linlin[1];Yang, Ruoou[3];Jiang, Zheng[3];Tian, Chao[1];Chen, Shangjun[1];Duan, Xuezhi[2];Chen, De[4];Wan, Ying[1]

机构：[1]Shanghai Normal Univ, Dept Chem, Key Lab Resource Chem, Shanghai Key Lab Rare Earth Funct Mat,Minist Educ, Shanghai 200234, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Adv Res Inst, Zhangjiang Natl Lab, Shanghai Synchrotron Radiat Facil, Shanghai 201210, Peoples R China;[4]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2021

卷号：8

期号：4

外文期刊名：NATIONAL SCIENCE REVIEW

收录：;EI(收录号：20212210440294);WOS:【SCI-EXPANDED(收录号:WOS:000651827200005)】；

基金：This work was supported by the National Natural Science Foundation of China (21773156 and 21503136), the Ministry of Education of China (PCSIRT IRT 16R49), the International Joint Laboratory on Resource Chemistry of China (IJLRC), the Shanghai Municipal Science and Technology Commission (17JC1404200) and the Shanghai Gaofeng & Gaoyuan Project for University Academic Program Development.

语种：英文

外文关键词：palladium interstitial catalyst; ordered mesoporous carbon; direct bisarylation; multi-site electron transfer; d-charge gain

摘要：The functionalization of otherwise unreactive C-H bonds adds a new dimension to synthetic chemistry, yielding useful molecules for a range of applications. Arylation has emerged as an increasingly viable strategy for functionalization of heteroarenes which constitute an important class of structural moieties for organic materials. However, direct bisarylation of heteroarenes to enable aryl-hetero aryl-aryl bond formation remains a formidable challenge, due to the strong coordination between heteroatom of N or S and transitional metals. Here we report Pd interstitial nano catalysts supported on ordered mesoporous carbon as catalysts for a direct and highly efficient bisarylation method for five-membered heteroarenes that allows for green and mild reaction conditions. Notably, in the absence of any base, ligands and phase transfer agents, high activity (turn-over frequency, TOF, up to 107 h(-1)) and selectivity (>99%) for the 2,5-bisarylation of five-membered heteroarenes are achieved in water. A combination of characterization reveals that the remarkable catalytic reactivity here is attributable to the parallel adsorption of heteroarene over Pd clusters, which breaks the barrier to electron transfer in traditional homogenous catalysis and creates dual electrophilic sites for awl radicals and adsorbate at C2 and C5 positions. The d-band filling at Pd sites shows a linear relationship with activation entropy and catalytic activity. The ordered mesopores facilitate the absence of a mass transfer effect. These findings suggest alternative synthesis pathways for the design, synthesis and understanding of a large number of organic chemicals by ordered mesoporous carbon supported palladium catalysts.