Electrochemical oxidative aminocarbonylation of terminal alkynes

作者:Zeng, L (Zeng, Li)[ 1 ] ; Li, HR (Li, Haoran)[ 1 ] ; Hu, JC (Hu, Jingcheng)[ 1 ] ; Zhang, DC (Zhang, Dongchao)[ 1 ] ; Hu, JY (Hu, Jiayu)[ 1 ] ; Peng, P (Peng, Pan)[ 1 ] ; Wang, SC (Wang, Shenchun)[ 1 ] ; Shi, RY (Shi, Renyi)[ 1 ] ; Peng, JQ (Peng, Jiaqi)[ 1 ] ; Pao, CW (Pao, Chih-Wen)[ 2 ] ...更多内容

NATURE CATALYSIS

卷: 3 期: 5 页: 438-445

DOI: 10.1038/s41929-020-0443-z

出版年: MAY 2020

在线发表日期: APR 2020

摘要

Oxidative carbonylation using CO/O-2 is an attractive strategy to construct carbonyl compounds, but the explosive limit of the gas mixture hampers its application. Now, this safety issue is overcome in the aminocarbonylation of alkynes by replacing the external oxidant O-2 by electrochemistry facilitating a mild and safe reaction.Palladium-catalysed oxidative carbonylation using oxygen as the oxidant is an economical approach; however, the gas mixture of CO and air has an explosive limit of 12.5-74.0% that could hamper extensive application of this process. Herein we report an electrochemical aminocarbonylation of alkynes under atmospheric pressure in an undivided cell without an external oxidant. The transformation has a broad substrate scope (83 examples) that involves primary amines and ammonium salts. Furthermore, mechanistic studies through cyclic voltammetry, in situ infrared and quick-scanning X-ray absorption fine structure spectroscopy reveal the reasons for this protocol proceeding smoothly under electrochemical conditions.

关键词

KeyWords Plus:CARBONYLATION REACTIONS; ORGANIC ELECTROSYNTHESIS; AMINES; CARBON; HYDROCARBONS; 2-YNAMIDES; EVOLUTION; CATALYSTS; GREEN

作者信息

通讯作者地址:

Wuhan University Wuhan Univ, Coll Chem & Mol Sci, IAS, Wuhan, Peoples R China.

通讯作者地址: Chen, YH; Lei, AW (通讯作者)

Wuhan Univ, Coll Chem & Mol Sci, IAS, Wuhan, Peoples R China.

地址:

[ 1 ]‎ Wuhan Univ, Coll Chem & Mol Sci, IAS, Wuhan, Peoples R China

[ 2 ]‎ Natl Synchrotron Radiat Res Ctr, Hsinchu, Taiwan

电子邮件地址:yihungchen@whu.edu.cn; aiwenlei@whu.edu.cn