Lewis Acid-Catalyzed Switchable Functionalization of <i>C</i> , <i>N</i> -Cyclic Ketimines with Vinyl Azides: Access to Diverse C(2)-Alkylated Pseudoindoxyls

Herein, a divergent coupling of indole-derived <i>C</i>,<i>N</i>-cyclic ketimines with vinyl azides is described for the synthesis of structurally diverse C(2)-alkylated pseudoindoxyls, especially α-indoxylacetamides, ketones, and acetonitrile derivatives. The Lewis acid-catalyzed divergent Schmidt and interrupted Schmidt-type pathways of the transient iminodiazonium ion intermediate enable vinyl azides to effectively function as surrogates for amides, ketones, and cyanomethanides. Furthermore, α-indoxylacetamides exhibited fluorescence properties, demonstrating an impressive fluorescence quantum yield.