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

摘要

Herein, a copper-catalyzed intramolecular cascade reaction of conjugated enynones to deliver substituted 1H-indenes is reported. The inexpensive and less toxic copper salt served as the only catalyst in the transformation, affording the 3-(2-furyl)-substituted 1H-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 6 pi cyclization of Cu-carbene and reductive elimination) and 1,5-hydrogen shift to provide the 1H-indenes.