Secondary Alcohol-Driven α-Olefination and α-Alkylation of Nitriles: Introducing a Heterogeneous Ru–Fe Bimetallic Catalyst

A catalytic strategy employing a Ru–Fe bimetallic heterogeneous catalyst is presented for α-olefination and α-alkylation of nitriles using secondary alcohols. Currently, catalysis for this reaction has been exclusively carried out with homogeneous catalysts, which generally achieve satisfactory yields but come with some drawbacks, including challenging recovery processes and limited characterization methods. In contrast, this heterogeneous catalyst not only simplifies recovery and can be reused for five cycles but also matches the yields of α-vinyl nitriles achieved by existing homogeneous catalysts. Additionally, this catalyst allows for some control over the production of either α-olefinated or α-alkylated nitriles under varying alkaline conditions. This work not only expands the catalytic systems for the synthesis of β-disubstituted vinyl nitriles using secondary alcohols but also demonstrates the potential of heterogeneous catalyst to broaden the scope of alcohols in acceptorless dehydrogenative coupling, showcasing the role of the bimetallic system in enhancing organic synthesis.