A Chiral Phenanthroline Ligand with a Hydrogen-Bonding Site: Application to the Enantioselective Amination of Methylene Groups
A Chiral Phenanthroline Ligand with a Hydrogen-Bonding Site: Application to the Enantioselective Amination of Methylene Groups
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DOI：
10.1021/jacs.0c02803
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发表时间：
2020-04-22
影响因子：
15
通讯作者：
Bach, Thorsten
中科院分区：
文献类型：
--
作者：
Annapureddy, Rajasekar Reddy;Jandl, Christian;Bach, Thorsten
报道了在各种喹诺酮和吡啶酮的脂肪族C3-取代基上发生的银催化胺化。C-H胺化反应以高位点选择性和对映体选择性进行（14个实施例，83- 97%ee）。其成功的关键是使用手性菲咯啉配体，该配体通过乙炔基连接体连接到八氢-1H-4，7-甲酰基异吲哚-1-酮的8位。AgPF 6（10摩尔%）作为银源，PhI=NNs作为氮宾前体，1，10-菲咯啉作为共配体。反应结果可以通过假设氮宾C-H插入氢键合的银络合物中来理解，其中单个C-H键暴露于催化反应中心。
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.