Diverse Transformation of Vinyl Azides with 2,2,6,6-Tetramethyl- N-oxopiperidinium.

A 2,2,6,6-tetramethyl- N-oxopiperidinium (TEMPO+)-mediated three-component diverse transformation of vinyl azides under metal-free conditions is described. The reaction protocols are operationally simple and conducted at ambient temperature, allowing to access various TEMPO-trapped ketones, amides, and α-alkoxyalkyl azides. Preliminary mechanistic studies indicate that an alkene radical cation-mediated radical-radical cross-coupling C-O bond formation could be involved.