Spirocyclic Products via Carbene Intermediates from Thermolysis of 1,2-Dialkynylpyrrole and 1,2-Diethynylimidazole

Abstract

The thermal rearrangements of 1,2-dialkynylimidazoles have been shown to lead to trapping products of cyclopenta[b]pyrazine carbene intermediates. Here we show that a similar rearrangement also occurs in the case of 1,2-diethynyl-1H-pyrrole, and that trapping the intermediate cyclopenta[b]pyridine carbene with solvent THF affords an ylide that undergoes a Stevens rearrangement to a spirocyclic product. An analogous rearrangement and trapping is observed for thermolysis of 1,2-dialkynylimidazoles in THF or 1,4-dioxane.