文献类型：期刊文献

英文题名：Heterogeneous Rhodium Single-Atom-Site Catalyst Enables Chemoselective Carbene N-H Bond Insertion

作者：Chen, Yuanjun[1,2,3,4];Zhang, Ruixue[1,2];Chen, Zhiwen[5];Liao, Jiangwen[6];Song, Xuedong[1,2];Liang, Xiao[3];Wang, Yu[7];Dong, Juncai[6];Singh, Chandra Veer[5];Wang, Dingsheng[3];Li, Yadong[3];Toste, F. Dean[8,9];Zhao, Jie[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China;[4]Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA;[5]Univ Toronto, Dept Mat Sci & Engn, Toronto, ON M5S 3E4, Canada;[6]Chinese Acad Sci, Inst High Energy Phys, Beijing Synchrotron Radiat Facil, Beijing 100049, Peoples R China;[7]Chinese Acad Sci, Zhangjiang Lab, Shanghai Adv Res Inst, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China;[8]Lawrence Berkeley Natl Lab, Chem Sci Div, Berkeley, CA 94720 USA;[9]Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

年份：2024

卷号：146

期号：15

起止页码：10847

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20241515890239);WOS:【SCI-EXPANDED(收录号:WOS:001200682000001)】；

基金：J.Z. acknowledges Project supported by Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), the Program of Introducing Talents of Discipline to Universities (B16017), and the National Natural Science Foundation of China (22301076). F.D.T. acknowledges support by the Director, Office of Science, Office of Basic Energy Science and the Division of Chemical Sciences, Geosciences, and Bioscience of the U.S. Department of Energy at Lawrence Berkeley National Laboratory (Grant DE-AC0205CH1123).

语种：英文

外文关键词：Aniline - Atoms - Catalysis - Catalyst selectivity - Density functional theory - Hydrogen bonds - Isomers - Ligands - Nitrogen - Phosphorus - Quantum chemistry - Transition metals

摘要：Transition-metal-catalyzed carbene insertion reactions of a nitrogen-hydrogen bond have emerged as robust and versatile methods for the construction of C-N bonds. While significant progress of homogeneous catalytic metal carbene N-H insertions has been achieved, the control of chemoselectivity in the field remains challenging due to the high electrophilicity of the metal carbene intermediates. Herein, we present an efficient strategy for the synthesis of a rhodium single-atom-site catalyst (Rh-SA) that incorporates a Rh atom surrounded by three nitrogen atoms and one phosphorus atom doped in a carbon support. This Rh-SA catalyst, with a catalyst loading of only 0.15 mol %, exhibited exceptional catalytic performance for heterogeneous carbene insertion with various anilines and heteroaryl amines in combination with diazo esters. Importantly, the heterogeneous catalyst selectively transformed aniline derivatives bearing multiple nucleophilic moieties into single N-H insertion isomers, while the popular homogeneous Rh-2(OAc)(4) catalyst produced a mixture of overfunctionalized side products. Additionally, similar selectivities for N-H bond insertion with a set of stereoelectronically diverse diazo esters were obtained, highlighting the general applicability of this heterogeneous catalysis approach. On the basis of density functional theory calculations, the observed selectivity of the Rh-SA catalyst was attributed to the insertion barriers and the accelerated proton transfer assisted by the phosphorus atom in the support. Overall, this investigation of heterogeneous metal-catalyzed carbene insertion underscores the potential of single-atom-site catalysis as a powerful and complementary tool in organic synthesis.