Copper–Nitrene Complexes in Catalytic CH Amination

作者：Yosra M. Badiei, Adriana Dinescu, Xuliang Dai, Robert M. Palomino, Frank W. Heinemann, Thomas R. Cundari, Timothy H. Warren · 发表于：Angewandte Chemie International Edition · 年份：2008 · DOI：10.1002/anie.200804304 · 被引用次数：351 · 研究领域：Synthesis and Catalytic Reactions、Catalytic C–H Functionalization Methods、Cyclopropane Reaction Mechanisms

Hydrocarbons activate! Isolable β-diketiminato dicopper–nitrene complexes such as 1 derived from the reaction of [{(Cl2NN)Cu}2(μ-benzene)] and 1-adamantylazide are potent towards nitrene insertion into unactivated sp3-hybridized CH bonds. 1 allows stoichiometric and catalytic intermolecular CH amination of hydrocarbons to give secondary amines (see scheme). Catalyst loadings as low as 0.05 mol % may be used.