Fiori Kristin Williams, Du Bois J
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
J Am Chem Soc. 2007 Jan 24;129(3):562-8. doi: 10.1021/ja0650450.
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 15N-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.
描述了苄基和叔碳C-H键分子间C-H胺化的反应方法。该过程使用起始烷烃作为限量试剂，通过立体定向插入对映体叔碳中心生成光学纯的四取代胺，对苄基氧化显示出高化学选择性，并能够轻松制备同位素富集的15N标记化合物。由此可以通过单一转化获得取代胺、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、反应化学选择性、活性氧化剂的性质以及催化剂失活途径相关的重要信息；这些研究也在此呈现。
