Radical Chain Isomerization of N-Sulfonyl Ynamides to Ketenimines and Its Application to Furan Dearomatization

A radical chain isomerization of N-sulfonyl ynamides to isolable ketenimines is developed, featuring mild reaction conditions, a high efficiency, similar to 100% atom economy, a broad substrate scope, and column chromatography-free workup in most cases. Meanwhile, an unprecedented dearomatization of furans is achieved by the radical chain isomerization-triggered aza-Claisen rearrangement, providing highly chemo-, regio-, stereo-, and diastereoselective access to functionalized quatemary nitrites.