Alkene Dicarbofunctionalisation via High-Valent Nickel Catalysis

Great advances have been made by leveraging high-valent Pd(II)/Pd(IV) catalysis in the areas of C–H activation and alkene difunctionalisation, thus representing a powerful approach for the construction of carbon-carbon and carbon-heteroatom bond. However, the catalytic reactions involving high-valent Ni(II)/Ni(IV) catalysis are largely underdeveloped. Here we report a Ni(II)-catalysed dicarbofunctionalisation of unactivated alkenes via high-valent Ni(II)/Ni(IV) catalysis. This dicarbofunctionalisation protocol provides a highly efficient and direct route towards vicinal substituted alkanes using primary, secondary, and tertiary amides, as well as secondary and tertiary amines as the native directing group under redox-neutral conditions that are challenging to access through conventional methods. The key to the success of this reaction is the use of a bulky β-diketone ligand, which could enable the insertion of alkene to aryl-Ni(II) species, stabilize the alkyl-Ni(II) species and inhibit the homolytic alkyl-Ni(II) cleavage. This dicarbofunctionalisation reaction features the use of native directing group, a broad substrate scope, and excellent scalability. The resulting Weinreb amide-derived products can be readily derivatized to a variety of ketones and aldehyde, which are fundamentally useful in synthetic chemistry. In addition, this protocol has been employed for the efficient preparation of several bioactive compounds, showcasing the significant synthetic values of our current method.