Indium(III)‐catalyzed Aza‐Conia‐Ene Reaction for the Synthesis of Indolizines

A new indium(III)‐catalyzed reaction for the synthesis of a series of indolizine scaffolds has been developed. This methodology was highly efficient, allowing a low catalyst loading of 2 mol % (down to 0.5 mol %) and rendering the products in high yields through a 5‐ exo ‐ dig aza‐Conia‐ene reaction. Furthermore, the possibility of incorporating an electrophile into the generated pyrrolidone ring in a one‐pot synergistic fashion was demonstrated. Finally, based on experimental observations, a mechanism proposal was outlined.