Frontispiece: Cyclopenta[b]annulation of Heteroarenes by Organocatalytic γ′[C(sp3)−H] Functionalization of Ynones

Abstract

Intramolecular Hydroalkylation Organocatalytic γ’[C(sp3)−H] functionalization of ynones has been achieved for the first time. Nucleophilic addition of an organophosphine to the designed ynones leads to the formation of heteroaryl‐based ortho‐quinodimethane (oQDM) intermediates, which undergo an unusual carbocyclization to provide functionalized cyclopenta‐fused heteroarenes. The present study can have potential implications on the development of new organocatalytic C(sp3)−H‐functionalization pathways.