Manganese-Catalyzed Divergent Markovnikov Addition and [2+2+2] Cycloaddition of 2‑Carbonyl Indanone with Terminal Alkyne

Herein, we report on manganese-catalyzed regioselective Markovnikov addition and [2+2+2] cycloaddition of 2-carbonyl indanones with terminal alkynes. This method provides an efficient approach for the construction of all-carbon quaternary centers and complex polycyclic hydrocarbon frameworks by the formation of new carbon–carbon single bonds in a regio- and stereoselective manner. Preliminary mechanistic experiments involving deuterium labeling, kinetic, catalytic, and stoichiometric reactions with plausible intermediates were performed to shed light on the reaction mechanism.