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Cu-Catalyzed Direct Amination of Cyclic Amides via C-OH Bond Activation Using DMF

Peng Chen, Kaixiu Luo, Xianglin Yu, Xu Yuan, Xiaoyu Liu, Jun Lin* and Yi Jin*

*School of Chemical Science and Technology, Yunnan University, Kunming 650091, P.R. China, Email: linjunynu.edu.cn, jinyiynu.edu.cn

P. Chen, K. Luo, X. Yu, X. Yuan, X. Liu, J. Lin, Y. Jin, Org. Lett., 2020, 22, 6547-6551.

DOI: 10.1021/acs.orglett.0c02320


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Abstract

A copper-catalyzed direct amination of cyclic amides in DMF forms aromatic heterocyclic amines with readily available reagents via a radical mechanism. The coordinating effect of the N1 atom provides assistance to the copper ions for the activation and amination of C-O bonds.

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Details

The document describes a study on a copper-catalyzed method for the direct amination of cyclic amides via C−OH bond activation using DMF. Traditional methods for converting cyclic amides to aromatic heterocyclic amines involve multiple steps and generate significant waste. This new approach is environmentally friendly and uses readily available reagents. The study found that the N1 atom in cyclic amides plays a crucial role in coordinating with copper ions to facilitate the activation and amination of C−O bonds. Various copper catalysts and oxidants were tested, with Cu(acac)2 and di-t-butyl peroxide (DTBP) providing the best yields. The method was effective with a range of amine substrates, resulting in moderate to excellent yields. The reaction mechanism involves the formation of a copper complex, followed by radical generation and subsequent C−N bond formation. The study also demonstrated the method's scalability and potential for further functionalization, making it a promising alternative for synthesizing aromatic heterocyclic amines. The research highlights the potential for developing more efficient and environmentally friendly catalytic processes in organic synthesis.


Key Words

quinazolines, DTBP


ID: J54-Y2020