Dearomative (3+2) Cycloadditions between Indoles and Vinyldiazo Species Enabled by a Red‐Shifted Chromium Photocatalyst

A direct dearomative photocatalyzed (3+2) cycloaddition between indoles and vinyldiazo reagents is described. The transformation is enabled by the development of a novel oxidizing Cr(III) photocatalyst, its specific reactivity attributed to increased absorptive properties over earlier Cr analogs and greater stability than Ru counterparts. A variety of fused indoline compounds are synthesized using this method, including densely functionalized ring systems that are feasible due to base‐free conditions. Experimental insights corroborate a cycloaddition initiated by nucleophilic attack at C3 of the indole radical cation by the vinyldiazo species.