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Metal-free C3-alkoxycarbonylation of quinoxalin-2(1H)-ones with carbazates as ecofriendly ester sources

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Abstract

Quinoxaline-3-carboxylates and analogues are prevalent key structural motifs in bioactive natural products and synthetic drugs. However, the practical protocol for preparation of these motifs from simple raw materials under mild conditions remains rare. In this article, we report a facile protocol for the efficient preparation of various quinoxaline-3-carbonyl compounds (30 examples, 63%–92%) through oxidation coupling of quinoxalin-2(1H)-ones with readily available carbazates (or acyl hydrazines) in the presence of K2S2O8 as an oxidant in metal- and base-free conditions. When tert-butyl carbazate was used as the coupling reagent, the decarboxylation product 3-(tert-butyl)-1-methylquinoxalin-2(1H)-one was obtained. The application of this process into a gram-scale synthesis can be easily accomplished. Mechanistic investigations reveal that the functionalization of quinoxalin-2 (1H)-ones via a free-radical pathway.

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Acknowledgements

This work was supported by the Hunan Provincial Natural Science Foundation of China (2019JJ20008) and the Construct Program of Applied Characteristic Discipline in Hunan University of Science and Engineering.

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Authors and Affiliations

  1. Department of Chemistry, Hunan University of Science and Engineering, Yongzhou, 425100, China

    Long-Yong Xie, Sha Peng, Tai-Gang Fan, Yan-Fang Liu, Li-Lin Jiang & Wei-Min He

  2. Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology, Xiangtan, 411201, China

    Meng Sun

  3. Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, Changsha University of Science and Technology, Changsha, 410114, China

    Xing-Xing Wang & Zhong Cao

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  1. Long-Yong Xie
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  2. Sha Peng
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Correspondence to Wei-Min He.

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Xie, LY., Peng, S., Fan, TG. et al. Metal-free C3-alkoxycarbonylation of quinoxalin-2(1H)-ones with carbazates as ecofriendly ester sources. Sci. China Chem. 62, 460–464 (2019). https://doi.org/10.1007/s11426-018-9446-1

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