Various spirooxindole‐benzo[d]oxazoles and dihydrobenzofurans were prepared in good to excellent yields by [3+2] cycloaddition and selective rearrangement of N‐vinyl oxindole nitrones and arynes under transition metal‐free conditions. Experimental results showed that the substituent on the nitrone N‐vinyl group controlled the [1,3]‐ or [3,3]‐rearrangement of their cycloadduct owing to its steric effect. The present method features broad substrate scope, good functional group tolerance, controllable [1,3]‐ or [3,3]‐rearrangement, and diverse oxindole scaffolds.

A variety of tetrahydro-5H-indolo[2,3-b]quinolines were prepared in 40–97% yields through a copper(II)-catalyzed cascade reaction of aza-o-quinone methides generated in situ from 2-(chloromethyl)anilines and indoles. Experimental results showed that the reaction underwent double 1,4-additions and sequential intramolecular cyclization. The present method features broad substrate scope, good functional group tolerance, and easy gram scalable preparation of indolo[2,3-b]quinolines.