Lebel Hélène, Huard Kim
Département de chimie, Université de Montréal, P.O. Box 6128, Station Downtown, Montréal, Québec, Canada, H3C 3J7.
Org Lett. 2007 Feb 15;9(4):639-42. doi: 10.1021/ol062953t. Epub 2007 Jan 23.
The rhodium-catalyzed intermolecular C-H insertion of the nitrene derived from 2,2,2-trichloroethyl-N-tosyloxycarbamate proceeded in good to excellent yields to produce a variety of Troc-protected amines. With cyclic aliphatic alkanes, it is possible to use only 2 equiv of substrate, whereas the reaction with aromatic alkanes is run neat. Not only does the nitrene insertion proceed in benzylic, secondary, and tertiary C-H bonds but also primary C-H insertion products were obtained in good yields. Finally, the use of chiral rhodium catalysts to provide an enantioselective version of this process is discussed. [reaction: see text].
铑催化的由2,2,2-三氯乙基-N-对甲苯磺酰氧基氨基甲酸酯衍生的氮烯的分子间C-H插入反应以良好至优异的产率进行，生成了多种Troc保护的胺。对于环状脂肪族烷烃，仅使用2当量的底物即可，而与芳香族烷烃的反应则 neat 进行。氮烯插入不仅发生在苄基、仲和叔C-H键上，而且伯C-H插入产物也能以良好的产率得到。最后，讨论了使用手性铑催化剂来实现该过程的对映选择性版本。[反应：见正文]
