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通过炔烃与光激发硝基芳烃的脱羰缩合实现无金属和无光催化剂的酰胺合成。

Metal and Photocatalyst-Free Amide Synthesis via Decarbonylative Condensation of Alkynes and Photoexcited Nitroarenes.

作者信息

Cui Rongqi, Liao Qian, Zhao Yuanxia, Wang Lifang, Zhang Yongqiang, Liu Shuyang, Gan Ziyu, Chen Yufei, Shi Yi, Shi Lei, Li Min, Jin Yunhe

机构信息

State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian 116024, China.

出版信息

Org Lett. 2024 Oct 4;26(39):8222-8227. doi: 10.1021/acs.orglett.4c02513. Epub 2024 Sep 24.

Abstract

Depending on the intrinsic photoactivity of nitroarenes, we herein developed a practical Brønsted acid-catalyzed decarbonylative amide synthesis from alkynes and photoexcited nitroarenes without any metal or photocatalyst. This method exhibited compatibility with water and air, broad substrate applicability, marvelous functional group tolerance, and wide applications in scale-up synthesis, late-stage functionalization, and total synthesis. Mechanism studies and DFT calculations supported that a 1,3,2-dioxazole intermediate was involved, and gaseous carbon monoxide was the only byproduct during amide construction.

摘要

基于硝基芳烃的固有光活性,我们在此开发了一种实用的布朗斯特酸催化的脱羰基酰胺合成方法,该方法以炔烃和光激发的硝基芳烃为原料,无需任何金属或光催化剂。该方法表现出与水和空气的兼容性、广泛的底物适用性、出色的官能团耐受性,并在放大合成、后期官能化和全合成中具有广泛应用。机理研究和密度泛函理论计算表明,反应涉及一个1,3,2-二恶唑中间体,并且在酰胺构建过程中气态一氧化碳是唯一的副产物。

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