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Scalable Electrocatalytic Intermolecular Acylcyanation and Aminocyanation of Alkenes

Xianqiang Kong*, Xiaohui Chen*, Yiyi Chen and Zhong-Yan Cao*

*Changzhou Institute of Technology, Changzhou 213032; Henan University, Kaifeng 475004, China, Email: kongxqczu.cn, chenxhczu.cn, zycaohenu.edu.cn

X. Kong, X. Chen, Y. Chen, Z.-Y. Cao, J. Org. Chem., 2022, 87, 7013-7021.

DOI: 10.1021/acs.joc.1c03134



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Abstract

The use of an electrophilic cyanation source enables electrocatalytic three-component acylcyanations and aminocyanations of a broad range of simple alkenes. The reaction offers high functional group tolerance and can easily be scaled up.

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Details

The article discusses the development of scalable electrocatalytic methods for the intermolecular acylcyanation and aminocyanation of alkenes. These methods are notable for their high functional group tolerance and ability to be scaled up. The key innovation is the use of an electrophilic cyanation source, which broadens the range of usable alkenes, including aliphatic ones. The protocol operates under mild conditions at room temperature and can be scaled to gram quantities. The study highlights the advantages of this method over traditional transition metal-catalyzed and photofacilitated approaches, which often require heating and are limited to styrenes. The optimized reaction conditions involve a platinum anode, carbon rod cathode, and specific solvents and bases, achieving high yields. The scope of the reaction was tested with various alkenes and α-oxocarboxylic acids, demonstrating good yields and functional group tolerance. The practical utility of the method was confirmed with a successful 10 mmol scale reaction. Additionally, the method was extended to aminocyanation using (PhSO2)2NH as the amination source. Mechanistic studies suggest the formation of acyl radicals, which add to olefins and are trapped by the cyanation reagent. The work represents a significant advancement in green and scalable synthetic methodologies for functionalized nitriles.


Key Words

cyanation, acylation, multicomponent reactions, electrochemistry


ID: J42-Y2022