Copper-Catalyzed Intramolecular Annulation of Conjugated Enynones to Substituted 1 H-Indenes and Mechanistic Studies.

Abstract

Herein, a copper-catalyzed intramolecular cascade reaction of conjugated enynones to deliver substituted 1 H-indenes is reported. The inexpensive and less toxic copper salt served as the only catalyst in the transformation, affording the 3-(2-furyl)-substituted 1 H-indenes in good to excellent yields under mild reaction conditions with broad functional group tolerance and making it highly appealing for synthetic organic chemistry. Notably, detailed DFT calculations have been carried out to elucidate that the reaction undergoes a copper-mediated 5- exo-dig cyclization of enynones to afford copper-(2-furyl)-carbene intermediate, followed by diene-carbene cyclization (one step but involving 6π cyclization of Cu-carbene and reductive elimination) and 1,5-hydrogen shift to provide the 1 H-indenes.