Catalytic intermolecular amination of C-H bonds: Method development and mechanistic insights
Catalytic intermolecular amination of C-H bonds: Method development and mechanistic insights
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DOI：
10.1021/ja0650450
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发表时间：
2007-01-24
影响因子：
15
通讯作者：
Du Bois, J.
中科院分区：
文献类型：
--
作者：
Fiori, Kristin Williams;Du Bois, J.
y描述了苄基和3度C-H键的分子间C-H胺化的反应方法。该方法使用起始烷烃作为限制试剂，通过立体特异性插入对映异构体3度中心得到光学纯的四取代胺，显示出对苄基氧化的高化学选择性，并且能够容易地制备同位素富集的N-15标记的化合物。因此，在单一转化中可以获得取代的胺、氨基醇和二胺。通过机理分析获得了与理解催化循环的初始步骤、反应的化学选择性、活性氧化剂的性质和催化剂失活途径有关的重要信息;这些研究也被提出。
y Reaction methodology for intermolecular C-H amination of benzylic and 3 degrees C-H bonds is described. This process uses the starting alkane as the limiting reagent, gives optically pure tetrasubstituted amines through stereospecific insertion into enantiomeric 3 degrees centers, displays high chemoselectivity for benzylic oxidation, and enables the facile preparation of isotopically enriched N-15-labeled compounds. Access to substituted amines, amino alcohols, and diamines is thereby made possible in a single transformation. Important information relevant to understanding the initial steps in the catalytic cycle, reaction chemoselectivity, the nature of the active oxidant, and pathways for catalyst inactivation has been gained through mechanistic analysis; these studies are also presented.