文献类型：期刊文献

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

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

机构：[1]Key Laboratory of Resource Chemistry of Ministry of Education,Shanghai Key Laboratory of Rare Earth Functional Materials,Department of Chemistry,Shanghai Normal University,Shanghai 200234,China;[2]State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;[3]Shanghai Synchrotron Radiation Facility,Zhangjiang National Lab,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201210,China;[4]Department of Chemical Engineering,Norwegian University of Science and Technology,Trondheim N-7491,Norway

年份：2021

卷号：8

期号：4

起止页码：149

中文期刊名：National Science Review

外文期刊名：国家科学评论（英文版）

收录：CSTPCD;;Scopus;CSCD:【CSCD2021_2022】；PubMed;

基金：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);the Shanghai Gaofeng&Gaoyuan Project for University Academic Program Development。

语种：英文

中文关键词：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-heteroaryl-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 nanocatalysts 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 aryl 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.