文献类型：期刊文献

英文题名：Effective Coordination Promoted Carbene N―H Bond Insertion on Heterogeneous Cu Catalyst

作者：Zhang, Ruixue[1,2];Sun, Mingze[3,4];Lu, Luan[1,2];You, Shu-Li[5];Niu, Zhiqiang[3,4];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, Frontiers Sci Ctr Materiobiol & Dynam Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai 200237, Peoples R China;[3]Tsinghua Univ, Dept Chem Engn, State Key Lab Chem Engn, Beijing 100084, Peoples R China;[4]Ordos Lab, Ordos 017010, Peoples R China;[5]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, 345 Lingling Lu, Shanghai 200032, Peoples R China

年份：2025

卷号：64

期号：51

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20254519447938);WOS:【SCI-EXPANDED(收录号:WOS:001605751000001)】；

基金：J. Z. thanks The National Natural Science Foundation of China (22572050, 22301076), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), The Program of Introducing Talents of Discipline to Universities (B16017) for funding support. Z. N. thanks the National Natural Science Foundation of China (22375113). The authors thank Prof. F. Dean Toste (U. C. Berkeley) and Prof. Haohong Duan (Tsinghua U.) for helpful discussions. J. Z. thanks Dr. Chenxi Guo for assisting in DFT study.

语种：英文

外文关键词：Carbene insertion; Cu nanowire; Heterogeneous carbene

摘要：In this study, we present a rationally designed Cu nanowire (NW) catalyst for carbene N & horbar;H bond insertion, addressing the challenges associated with highly coordinative aliphatic amines. The heterogeneous Cu NW catalyst with well-defined structures efficiently catalyzed carbene insertion reactions between various alpha-aryl diazoesters and aliphatic amines including monoethanolamine (MEA), achieving moderate to high yields. Infrared spectroscopy analysis and theoretical studies confirm the strong coordination of MEA on the surface of the Cu NW. Comprehensive kinetic studies reveal that both the two substrates and Cu NW were involved in the rate-determining step (RDS). Notably, the observed second-order dependence on Cu NW suggests that two identical Cu atoms participated in the RDS, one coordinating with the carbene carbon and the other binding with the amine nitrogen. A Hammett-plot study with 4-substituted benzylamines reveal that amines bearing electron-donating groups reacted significantly more slowly than those bearing electron-withdrawing groups, supporting a concerted N & horbar;H carbene insertion mechanism. Collectively, these findings elucidate the exceptional catalytic performance of Cu NW in carbene N & horbar;H bond insertion reactions, further underscoring the significance of heterogeneous catalysts in organic transformations.