[3 + 4] Annulation of Bromoenals and 1,2-Benzenedithiol: Base-Promoted [2 + 4] Reaction and N-Heterocyclic Carbene-Catalyzed Ring-Expansion.

The [3 + 4] and [2 + 4] annulations of bromoenals and 1,2-benzenedithiol were developed in the presence or absence of N-heterocyclic carbene, respectively. Control experiment and kinetic investigation revealed the [3 + 4] annulation involves the base-promoted [2 + 4] annulation and the following carbene-catalyzed ring-expansion.