34197-75-6Relevant academic research and scientific papers
Cobalt(II)-catalyzed intermolecular benzylic C-H amination with 2,2,2-trichloroethoxycarbonyl azide (TrocN3)
Lu, Hongjian,Subbarayan, Velusamy,Tao, Jingran,Zhang, X. Peter
experimental part, p. 389 - 393 (2010/04/04)
2,2,2-Trichloroethoxycarbonyl azide (TrocN3) is an effective nitrene source for cobalt(II)-catalyzed intermolecular nitrene insertion of C-H bonds. Among different metalloporphyrins studied, Co(II)(TPP) was shown to be a competent catalyst for the selective amination of various benzylic C-H bonds under mild conditions without the need of other reagents or additives, forming the desired Trocprotected amines in moderate to high yields with nitrogen gas as the only byproduct.
N-tosyloxycarbamates as reagents in rhodium-catalyzed C-H amination reactions
Huard, Kim,Lebel, Helene
supporting information; experimental part, p. 6222 - 6230 (2009/05/27)
Metal nitrenes for use in C-H insertion reactions were obtained from N-tosyloxycarbamates in the presence of an inorganic base and a rhodium(II) dimer complex catalyst. The C-H amination reaction proceeds smoothly, and the potassium tosylate that forms as a byproduct is easily removed by filtration or an aqueous workup. This new methodology allows the amination of ethereal, benzylic, tertiary, secondary, and even primary C-H bonds. The intramolecular reaction provides an interesting route to various substituted oxazolidinones, whereas the intermolecular reaction gives trichloroethoxycarbonyl-protected amines that can be isolated with moderate to excellent yields and that cleave easily to produce the corresponding free amine. The development, scope, and limitations of the reactions are discussed herein. Isotopic effects and the electronic nature of the transition state are used to discuss the mechanism of the reaction.
