Copper-Catalyzed Intermolecular [2 + 2 + 2] Annulation of Diynes with Alkynes: Construction of Carbazoles.

Transition-metal-catalyzed [2 + 2 + 2] annulation of alkynes is an efficient pathway for the synthesis of aromatic compounds. However, most of the established methods require noble metal catalysts. Herein, we report a copper-catalyzed intermolecular [2 + 2 + 2] annulation of diynes with alkynes through vinyl cation intermediates, enabling the atom-economical preparation of biologically important carbazole skeletons. The reaction shows good regioselectivity in the reaction of aryl(alkyl)alkynes. Moreover, preliminary results have also been obtained for the related catalytic atroposelective transformation. This reaction represents a rare example of non-noble-metal-catalyzed intermolecular [2 + 2 + 2] annulation of ynamides through the vinyl cation pathway.