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Abstract
A radical chain isomerization of N-sulfonyl ynamides to isolable ketenimines is developed, featuring mild reaction conditions, a high efficiency, ∼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 quaternary nitriles.
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