Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis

Abstract Electro/photocatalytic C-N coupling acts as a key build-block to the next generation of chemicals like amides for wide applications in energy, pharmaceuticals and chemical industries. However, the uncontrolled intermediates coupling challenges the efficient amide production regarding yield...

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Main Authors: Xin Li, Weiping Yang, Junping Yue, Jieyuan Li, Shujie Shen, Ruimin Chen, Jielin Wang, Huimin Dan, Dagang Yu, Fan Dong
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-58840-0
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author Xin Li
Weiping Yang
Junping Yue
Jieyuan Li
Shujie Shen
Ruimin Chen
Jielin Wang
Huimin Dan
Dagang Yu
Fan Dong
author_facet Xin Li
Weiping Yang
Junping Yue
Jieyuan Li
Shujie Shen
Ruimin Chen
Jielin Wang
Huimin Dan
Dagang Yu
Fan Dong
author_sort Xin Li
collection DOAJ
description Abstract Electro/photocatalytic C-N coupling acts as a key build-block to the next generation of chemicals like amides for wide applications in energy, pharmaceuticals and chemical industries. However, the uncontrolled intermediates coupling challenges the efficient amide production regarding yield or selectivity. Here we propose a photocatalytic radical addition route, where the fundamental active species, including oxygen and photogenerated electron-hole pairs, are regulated for selective intermediates generation and efficient acetamide synthesis from mild co-oxidation of CH3CH2OH and NH3. Sufficient CH3CH2OH is provided to accumulate the stable intermediate (CH3CHO). Meanwhile, the limited NH3 concentration ensures the controllable generation and fast addition of the transient radical (●NH2) on CH3CHO. Through the directed coupling of stable-transient intermediates, the acetamide synthesis rate is pushed forward to a hundred-mmol level (105.61 ± 4.86 mmol·gcat −1·h−1) with a selectivity of 99.17% ± 0.39%, reaching a gram-scale yield (1.82 g) of acetamide. These results illuminate valuable opportunities for the photocatalysis-driven synthetic industry.
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issn 2041-1723
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spelling doaj-art-3a6be3fd93694225bf9f04d290c6010f2025-08-20T02:28:10ZengNature PortfolioNature Communications2041-17232025-04-011611910.1038/s41467-025-58840-0Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesisXin Li0Weiping Yang1Junping Yue2Jieyuan Li3Shujie Shen4Ruimin Chen5Jielin Wang6Huimin Dan7Dagang Yu8Fan Dong9Research Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaKey Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan UniversityResearch Center for Carbon-Neutral Environmental & Energy Technology, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of ChinaAbstract Electro/photocatalytic C-N coupling acts as a key build-block to the next generation of chemicals like amides for wide applications in energy, pharmaceuticals and chemical industries. However, the uncontrolled intermediates coupling challenges the efficient amide production regarding yield or selectivity. Here we propose a photocatalytic radical addition route, where the fundamental active species, including oxygen and photogenerated electron-hole pairs, are regulated for selective intermediates generation and efficient acetamide synthesis from mild co-oxidation of CH3CH2OH and NH3. Sufficient CH3CH2OH is provided to accumulate the stable intermediate (CH3CHO). Meanwhile, the limited NH3 concentration ensures the controllable generation and fast addition of the transient radical (●NH2) on CH3CHO. Through the directed coupling of stable-transient intermediates, the acetamide synthesis rate is pushed forward to a hundred-mmol level (105.61 ± 4.86 mmol·gcat −1·h−1) with a selectivity of 99.17% ± 0.39%, reaching a gram-scale yield (1.82 g) of acetamide. These results illuminate valuable opportunities for the photocatalysis-driven synthetic industry.https://doi.org/10.1038/s41467-025-58840-0
spellingShingle Xin Li
Weiping Yang
Junping Yue
Jieyuan Li
Shujie Shen
Ruimin Chen
Jielin Wang
Huimin Dan
Dagang Yu
Fan Dong
Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis
Nature Communications
title Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis
title_full Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis
title_fullStr Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis
title_full_unstemmed Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis
title_short Photocatalytic C-N coupling from stable and transient intermediates for gram-scale acetamide synthesis
title_sort photocatalytic c n coupling from stable and transient intermediates for gram scale acetamide synthesis
url https://doi.org/10.1038/s41467-025-58840-0
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