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Updated: May 29, 2025

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to
Takehiro Matsuyama1, Takafumi Yatabe2,3, Tomohiro Yabe1
1Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
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.
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