Reductive C−C Coupling from α,β‐Unsaturated Nitriles by Intercepting Keteniminates

We present an atom-economic strategy to catalytically generate and intercept nitrile anion equivalents using hydrogen transfer catalysis. Addition of α,β-unsaturated nitriles to a pincer-based Ru-H complex affords structurally characterized κ-N-coordinated keteniminates by selective 1,4-hydride transfer. When generated in situ under catalytic hydrogenation conditions, electrophilic addition to the keteniminate was achieved using anhydrides to provide α-cyanoacetates in high yields. This work represents a new application of hydrogen transfer catalysis using α,β-unsaturated nitriles for reductive C-C coupling reactions.