Expanding the scope of C-H amination through catalyst design
Expanding the scope of C-H amination through catalyst design
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DOI：
10.1021/ja0446294
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发表时间：
2004-12-01
影响因子：
15
通讯作者：
Du Bois, J
中科院分区：
文献类型：
--
作者：
Espino, CG;Fiori, KW;Du Bois, J
对Rh介导的C-H胺化反应机理的分析导致了一种非常有效的双核Rh催化剂的开发，该催化剂衍生自1，3-苯二丙酸。这种独特的配合物Rh 2（esp）2能够促进分子内和分子间的C-H氧化反应，并且在所有情况下都上级Rh 2（O2 CtBu）4。第一次，C-H插入描述与尿素和磺酰胺底物，得到1，2-和1，3-二胺衍生物，分别。此外，苄基和仲C-H键的分子间胺化被证明即使在起始烷烃用作限制试剂的条件下也能有效地进行。
Analysis of the mechanism for Rh-mediated C−H amination has led to the development of a remarkably effective dinuclear Rh catalyst derived from 1,3-benzenedipropionic acid. This unique complex, Rh2(esp)2, is capable of promoting both intra- and intermolecular C−H oxidation reactions, and in all cases is superior to Rh2(O2CtBu)4. For the first time, C−H insertion is described with urea and sulfamide substrates to give 1,2- and 1,3-diamine derivatives, respectively. In addition, intermolecular amination of benzylic and secondary C−H bonds is shown to proceed efficiently even under conditions in which the starting alkane is employed as the limiting reagent.