Catalytic Claisen Rearrangement by Intercepting Ketenimines with Propargylic Alcohols: A Strategy to Generate and Transform Ketenimines from Radicals.

An efficient strategy for facilitating the cross-coupling of two radicals has been established via the coordination of a radical with a metal catalyst. This strategy provides a remarkable ability to harness the reactivity of nitrile-containing azoalkanes and enables a novel cascade reaction with nitrile-containing azoalkanes and propargylic alcohols to be established. By using this reaction, a range of acetylenic and allenic amides were obtained that provides a versatile platform for further derivatizations.