文献类型：期刊文献

英文题名：Heterogeneous Iridium-Catalyzed Carbene N-H Bond Insertion with α-Alkyl Diazo Esters

作者：Guo, Ping[1,2];Chen, Yan[1,2];Tao, Lei[3];Ji, Shufang[4,5];Zhang, Ruixue[1,2];Zhang, Zedong[4];Liang, Xiao[4];Wang, Dingsheng[4];Li, Yadong[4];Zhao, Jie[1,2,6]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Sci 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]Univ Chinese Acad Sci, Beijing 100049, Peoples R China;[4]Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China;[5]Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada;[6]Tsinghua Univ, Dept Chem, Key Lab Bioorgan Phosphorus Chem & Chem Biol, Minist Educ, Beijing 100084, Peoples R China

年份：2024

卷号：14

期号：7

起止页码：4690

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20241215757395);WOS:【SCI-EXPANDED(收录号:WOS:001184911400001)】；

基金：J.Z. acknowledges the project supported by the 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). Y.L. acknowledges the project supported by the NSFC Center for Single-Atom Catalysis (22388102).

语种：英文

外文关键词：heterogeneous; carbene insertion; iridium; selectivity; catalysis.

摘要：A heterogeneous iridium single-atom site catalyst (Ir-SA) was synthesized and investigated in catalyzing the carbene insertion reaction with challenging alpha-alkyl diazo ester substrates. With only 0.23 mol % catalyst loading, our Ir-SA demonstrated remarkable performance in heterogeneous carbene N-H bond insertion reactions involving various (hetero) aryl amines coupled with alpha-alkyl diazo esters. Notably, in the case of using a chiral diamino substrate with two reactive sites, Ir-SA exhibited high selectivity toward single carbene N-H insertion, leading to the generation of a class of unsymmetric chiral diamino ligands. Further mechanism study revealed that the lower activation barrier associated with the single N-H bond insertion step, as compared to either beta-hydride elimination or downstream dual N-H bond insertion, accounted for the remarkable selectivity observed in this carbene insertion reaction catalyzed by Ir-SA.