Intermolecular C(sp3)-H Amination of Complex Molecules

被引：79
|
作者：
Chiappini, Nicholas D. [1 ]
Mack, James B. C. [1 ]
Du Bois, J. [1 ]
机构：
[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 18期
基金：
美国国家科学基金会;
关键词：
amination; C-H oxidation; reaction mechanisms; rhodium; sulfamates; C-H AMINATION; NITRENE TRANSFER-REACTIONS; BOND AMINATION; CATALYST; FUNCTIONALIZATION; AZIRIDINATION; RH-2(ESP)(2); CARBOXYLATE; CHALLENGES; ASSIGNMENT;
D O I：
10.1002/anie.201713225
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A general and operationally convenient method for intermolecular amination of C(sp(3))-H bonds is described. This technology allows for efficient functionalization of complex molecules, including numerous pharmaceutical targets. The combination of pivalonitrile as a solvent, Al2O3 as an additive, and phenyl sulfamate as a nitrogen source affords differential reaction performance and substrate scope. Mechanistic data strongly implicate a pathway for catalyst decomposition that initiates with solvent oxidation, thus providing rationale for the marked influence of pivalonitrile on this reaction process.
引用
收藏
页码：4956 / 4959
页数：4
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