Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents

Abstract Carbon-heteroatom bond (especially for C-N bond) formation through nickel catalysis has seen significant development. Well-established Ni(0)/Ni(II) redox cycle and photoinduced Ni(I)/Ni(III) redox cycle have been the dominant mechanisms. We report a thermally driven Ni-catalyzed method for...

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Main Authors: Qianqian Chang, Qini Li, Yi-Hui Deng, Tian-Yu Sun, Yun-Dong Wu, Leifeng Wang
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-58438-6
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author Qianqian Chang
Qini Li
Yi-Hui Deng
Tian-Yu Sun
Yun-Dong Wu
Leifeng Wang
author_facet Qianqian Chang
Qini Li
Yi-Hui Deng
Tian-Yu Sun
Yun-Dong Wu
Leifeng Wang
author_sort Qianqian Chang
collection DOAJ
description Abstract Carbon-heteroatom bond (especially for C-N bond) formation through nickel catalysis has seen significant development. Well-established Ni(0)/Ni(II) redox cycle and photoinduced Ni(I)/Ni(III) redox cycle have been the dominant mechanisms. We report a thermally driven Ni-catalyzed method for C-N bond formation between haloarenes and B2N4 reagents, yielding N,N-dialkylaniline derivatives in good to excellent yields with broad functional group tolerance under base-free conditions. The catalytic protocol is useful for base-sensitive structures and late-stage modifications of complex molecules. Detailed mechanistic studies and density functional theory (DFT) calculations indicate that a Ni(I)/Ni(III) redox cycle is preferred in the C-N coupling process, and B2N4 reagent serves both as a single electron transfer donor and a N,N-dialkylation source.
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id doaj-art-751ebc0522ed4377a54de6c2df489214
institution DOAJ
issn 2041-1723
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publishDate 2025-04-01
publisher Nature Portfolio
record_format Article
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spelling doaj-art-751ebc0522ed4377a54de6c2df4892142025-08-20T03:07:43ZengNature PortfolioNature Communications2041-17232025-04-0116111110.1038/s41467-025-58438-6Nickel catalyzed C-N coupling of haloarenes with B2N4 reagentsQianqian Chang0Qini Li1Yi-Hui Deng2Tian-Yu Sun3Yun-Dong Wu4Leifeng Wang5School of Pharmaceutical Sciences (Shenzhen), Shenzhen Campus of Sun Yat-sen UniversitySchool of Pharmaceutical Sciences (Shenzhen), Shenzhen Campus of Sun Yat-sen UniversityKey Laboratory of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Shenzhen Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate SchoolKey Laboratory of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Shenzhen Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate SchoolKey Laboratory of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Shenzhen Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate SchoolSchool of Pharmaceutical Sciences (Shenzhen), Shenzhen Campus of Sun Yat-sen UniversityAbstract Carbon-heteroatom bond (especially for C-N bond) formation through nickel catalysis has seen significant development. Well-established Ni(0)/Ni(II) redox cycle and photoinduced Ni(I)/Ni(III) redox cycle have been the dominant mechanisms. We report a thermally driven Ni-catalyzed method for C-N bond formation between haloarenes and B2N4 reagents, yielding N,N-dialkylaniline derivatives in good to excellent yields with broad functional group tolerance under base-free conditions. The catalytic protocol is useful for base-sensitive structures and late-stage modifications of complex molecules. Detailed mechanistic studies and density functional theory (DFT) calculations indicate that a Ni(I)/Ni(III) redox cycle is preferred in the C-N coupling process, and B2N4 reagent serves both as a single electron transfer donor and a N,N-dialkylation source.https://doi.org/10.1038/s41467-025-58438-6
spellingShingle Qianqian Chang
Qini Li
Yi-Hui Deng
Tian-Yu Sun
Yun-Dong Wu
Leifeng Wang
Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents
Nature Communications
title Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents
title_full Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents
title_fullStr Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents
title_full_unstemmed Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents
title_short Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents
title_sort nickel catalyzed c n coupling of haloarenes with b2n4 reagents
url https://doi.org/10.1038/s41467-025-58438-6
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AT yihuideng nickelcatalyzedcncouplingofhaloareneswithb2n4reagents
AT tianyusun nickelcatalyzedcncouplingofhaloareneswithb2n4reagents
AT yundongwu nickelcatalyzedcncouplingofhaloareneswithb2n4reagents
AT leifengwang nickelcatalyzedcncouplingofhaloareneswithb2n4reagents