Pd-Catalyzed\nHydrocyanation of Methylenecyclopropanes:\nA Highly Selective Ring-Opening Access to 2‑Substituted Allylic\nNitriles

Transition-metal-catalyzed hydrofunctionalization of\nmethylenecyclopropanes\npresents a useful but challenging transformation due to the complex\nselectivity and multiple reaction pathways. We describe herein an\nunprecedented highly efficient and selective palladium-catalyzed hydrocyanation\nof methylenecyclopropanes to give various 2-substituted allylic nitriles.\nMechanistic studies demonstrated that the transformation may undergo\nMarkovnikov-type hydrometalation and β-carbon elimination.