A Chiral Phenanthroline Ligand with a Hydrogen-Bonding Site: Application to the Enantioselective Amination of Methylene Groups

被引：35

作者：

Annapureddy, Rajasekar Reddy ^{[1
,2
]}

Jandl, Christian ^{[1
,2
]}

Bach, Thorsten ^{[1
,2
]}

机构：

[1] Tech Univ Munich, Dept Chem, D-85747 Garching, Germany

[2] Tech Univ Munich, CRC, D-85747 Garching, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2020年 / 142卷 / 16期

关键词：

NITRENE TRANSFER; AMIDATION; CATALYST; AZIRIDINATION; RUTHENIUM;

D O I：

10.1021/jacs.0c02803

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A silver-catalyzed amination is reported that occurs at the aliphatic C3-substituent of various quinolones and pyridones. The C-H amination reaction proceeded with high site- and enantioselectivity (14 examples, 83-97% ee). The key to its success is the use of a chiral phenanthroline ligand that is attached via an ethynyl linker to the 8-position of octahydro-1H-4,7-methanoisoindol-1-one. AgPF6 (10 mol %) served as the silver source, PhI=NNs as the nitrene precursor, and 1,10-phenanthroline as the coligand. The reaction outcome can be understood by assuming a nitrene C-H insertion within a hydrogen-bonded silver complex in which a single C-H bond is exposed to the catalytic reaction center.

引用

页码：7374 / 7378

页数：5

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