N-tosyloxycarbamates as reagents in rhodium-catalyzed C-H Amination reactions
N-tosyloxycarbamates as reagents in rhodium-catalyzed C-H Amination reactions
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DOI：
10.1002/chem.200702027
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发表时间：
2008-01-01
影响因子：
4.3
通讯作者：
Lebel, Helene
中科院分区：
文献类型：
--
作者：
Huard, Kim;Lebel, Helene
在无机碱和铑（11）二聚体催化剂的存在下，从n -甲氧基氨基甲酸酯中得到用于碳氢插入反应的金属亚硝基烯。C-H胺化反应进行顺利，而作为副产物形成的tosy酸钾很容易通过过滤或水处理去除。这种新的方法允许乙醛，苯基，叔，仲，甚至伯碳-氢键的胺化。分子内反应为生成各种取代的恶唑烷酮提供了一条有趣的途径，而分子间反应则产生了三氯乙氧羰基保护胺，这些胺可以以中等到优异的收率分离出来，并且很容易裂解产生相应的游离胺。本文讨论了这些反应的发展、范围和局限性。利用同位素效应和过渡态的电子性质来讨论反应的机理。
Metal nitrenes for use in C-H insertion reactions were obtained from N-tosyloxycarbamates in the presence of an inorganic base and a rhodium(11) 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 trichloroetboxycarbonyl-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.