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Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds

[Image: see text] The C–N bond cleavage represents one kind of important organic and biochemical transformation, which has attracted great interest in recent years. The oxidative cleavage of C–N bonds in N,N-dialkylamines into N-alkylamines has been well documented, but it is challenging in the furt...

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Autores principales: Qin, Jingzhong, Han, Bo, Lu, Xiaomei, Nie, Jiabao, Xian, Chensheng, Zhang, Zehui
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10052240/
https://www.ncbi.nlm.nih.gov/pubmed/37006771
http://dx.doi.org/10.1021/jacsau.2c00605
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author Qin, Jingzhong
Han, Bo
Lu, Xiaomei
Nie, Jiabao
Xian, Chensheng
Zhang, Zehui
author_facet Qin, Jingzhong
Han, Bo
Lu, Xiaomei
Nie, Jiabao
Xian, Chensheng
Zhang, Zehui
author_sort Qin, Jingzhong
collection PubMed
description [Image: see text] The C–N bond cleavage represents one kind of important organic and biochemical transformation, which has attracted great interest in recent years. The oxidative cleavage of C–N bonds in N,N-dialkylamines into N-alkylamines has been well documented, but it is challenging in the further oxidative cleavage of C–N bonds in N-alkylamines into primary amines due to the thermally unfavorable release of α-position H from N–C(α)–H and the paralleling side reactions. Herein, a biomass-derived single Zn atom catalyst (ZnN(4)-SAC) was discovered to be a robust heterogeneous non-noble catalyst for the oxidative cleavage of C–N bonds in N-alkylamines with O(2) molecules. Experimental results and DFT calculation revealed that ZnN(4)-SAC not only activates O(2) to generate superoxide radicals (·O(2)(–)) for the oxidation of N-alkylamines to generate imine intermediates (C=N), but the single Zn atoms also served as the Lewis acid sites to promote the cleavage of C=N bonds in imine intermediates, including the first addition of H(2)O to generate α-hydroxylamine intermediates and the following C–N bond cleavage via a H atom transfer process.
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spelling pubmed-100522402023-03-30 Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds Qin, Jingzhong Han, Bo Lu, Xiaomei Nie, Jiabao Xian, Chensheng Zhang, Zehui JACS Au [Image: see text] The C–N bond cleavage represents one kind of important organic and biochemical transformation, which has attracted great interest in recent years. The oxidative cleavage of C–N bonds in N,N-dialkylamines into N-alkylamines has been well documented, but it is challenging in the further oxidative cleavage of C–N bonds in N-alkylamines into primary amines due to the thermally unfavorable release of α-position H from N–C(α)–H and the paralleling side reactions. Herein, a biomass-derived single Zn atom catalyst (ZnN(4)-SAC) was discovered to be a robust heterogeneous non-noble catalyst for the oxidative cleavage of C–N bonds in N-alkylamines with O(2) molecules. Experimental results and DFT calculation revealed that ZnN(4)-SAC not only activates O(2) to generate superoxide radicals (·O(2)(–)) for the oxidation of N-alkylamines to generate imine intermediates (C=N), but the single Zn atoms also served as the Lewis acid sites to promote the cleavage of C=N bonds in imine intermediates, including the first addition of H(2)O to generate α-hydroxylamine intermediates and the following C–N bond cleavage via a H atom transfer process. American Chemical Society 2023-02-16 /pmc/articles/PMC10052240/ /pubmed/37006771 http://dx.doi.org/10.1021/jacsau.2c00605 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Qin, Jingzhong
Han, Bo
Lu, Xiaomei
Nie, Jiabao
Xian, Chensheng
Zhang, Zehui
Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds
title Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds
title_full Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds
title_fullStr Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds
title_full_unstemmed Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds
title_short Biomass-Derived Single Zn Atom Catalysts: The Multiple Roles of Single Zn Atoms in the Oxidative Cleavage of C–N Bonds
title_sort biomass-derived single zn atom catalysts: the multiple roles of single zn atoms in the oxidative cleavage of c–n bonds
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10052240/
https://www.ncbi.nlm.nih.gov/pubmed/37006771
http://dx.doi.org/10.1021/jacsau.2c00605
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