Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles
Abstract The dehydrogenative aromatisation of cyclohexanone derivatives has had a transformative influence on the synthesis of aromatic compounds because functional groups can be easily introduced at desired positions via classic organic reactions without being limited by ortho-, meta- or para-orien...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56361-4 |
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| _version_ | 1823861816892063744 |
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| author | Takehiro Matsuyama Takafumi Yatabe Tomohiro Yabe Kazuya Yamaguchi |
| author_facet | Takehiro Matsuyama Takafumi Yatabe Tomohiro Yabe Kazuya Yamaguchi |
| author_sort | Takehiro Matsuyama |
| collection | DOAJ |
| description | Abstract The dehydrogenative aromatisation of cyclohexanone derivatives has had a transformative influence on the synthesis of aromatic compounds because functional groups can be easily introduced at desired positions via classic organic reactions without being limited by ortho-, meta- or para-orientations. However, research is still limited on acceptorless dehydrogenative aromatisation, especially with regard to nonprecious-metal catalysts. Ni is a promising candidate catalyst as a congener of Pd, but thermally Ni-catalysed dehydrogenative aromatisation has not been reported even in an oxidative manner because of the difficulty of β-hydride elimination and the fast re-insertion of Ni–H species. Here, we report a CeO2-supported Ni(0) nanoparticle catalyst for acceptorless dehydrogenative aromatisation of cyclohexanone derivatives. This catalyst is widely applicable to various compounds such as cyclohexanols, cyclohexylamines, N-heterocycles, enamines and β-heteroatom-substituted ketones. Through various experiments, we demonstrate that the present reaction was achieved by the concerted catalysis utilizing metal ensembles unique to supported metal nanoparticle catalysts. |
| format | Article |
| id | doaj-art-81cd3aa6156943438dec11760e687dbb |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-81cd3aa6156943438dec11760e687dbb2025-02-09T12:44:00ZengNature PortfolioNature Communications2041-17232025-02-0116111210.1038/s41467-025-56361-4Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticlesTakehiro Matsuyama0Takafumi Yatabe1Tomohiro Yabe2Kazuya Yamaguchi3Department of Applied Chemistry, School of Engineering, The University of TokyoDepartment of Applied Chemistry, School of Engineering, The University of TokyoDepartment of Applied Chemistry, School of Engineering, The University of TokyoDepartment of Applied Chemistry, School of Engineering, The University of TokyoAbstract The dehydrogenative aromatisation of cyclohexanone derivatives has had a transformative influence on the synthesis of aromatic compounds because functional groups can be easily introduced at desired positions via classic organic reactions without being limited by ortho-, meta- or para-orientations. However, research is still limited on acceptorless dehydrogenative aromatisation, especially with regard to nonprecious-metal catalysts. Ni is a promising candidate catalyst as a congener of Pd, but thermally Ni-catalysed dehydrogenative aromatisation has not been reported even in an oxidative manner because of the difficulty of β-hydride elimination and the fast re-insertion of Ni–H species. Here, we report a CeO2-supported Ni(0) nanoparticle catalyst for acceptorless dehydrogenative aromatisation of cyclohexanone derivatives. This catalyst is widely applicable to various compounds such as cyclohexanols, cyclohexylamines, N-heterocycles, enamines and β-heteroatom-substituted ketones. Through various experiments, we demonstrate that the present reaction was achieved by the concerted catalysis utilizing metal ensembles unique to supported metal nanoparticle catalysts.https://doi.org/10.1038/s41467-025-56361-4 |
| spellingShingle | Takehiro Matsuyama Takafumi Yatabe Tomohiro Yabe Kazuya Yamaguchi Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles Nature Communications |
| title | Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles |
| title_full | Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles |
| title_fullStr | Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles |
| title_full_unstemmed | Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles |
| title_short | Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles |
| title_sort | ni catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles |
| url | https://doi.org/10.1038/s41467-025-56361-4 |
| work_keys_str_mv | AT takehiromatsuyama nicatalysedacceptorlessdehydrogenativearomatisationofcyclohexanonesenabledbyconcertedcatalysisspecifictosupportednanoparticles AT takafumiyatabe nicatalysedacceptorlessdehydrogenativearomatisationofcyclohexanonesenabledbyconcertedcatalysisspecifictosupportednanoparticles AT tomohiroyabe nicatalysedacceptorlessdehydrogenativearomatisationofcyclohexanonesenabledbyconcertedcatalysisspecifictosupportednanoparticles AT kazuyayamaguchi nicatalysedacceptorlessdehydrogenativearomatisationofcyclohexanonesenabledbyconcertedcatalysisspecifictosupportednanoparticles |