Catalytic Enantioselective Protonation of Gold Enolates Enabled by Cooperative Gold(I) Catalysis

Enantioselective protonation is a versatile approach to the construction of tertiary alpha-stereocenters, which are common structural motifs in various natural products and biologically relevant compounds. Herein we report a mild access to these chiral centers using cooperative gold(I) catalysis. From cyclic ketone enol carbonates, this asymmetric catalysis provides highly enantioselective access to cyclic ketones featuring an alpha tertiary chiral center, including challenging 2-methylsuberone. In combination with the gold-catalyzed formation of cyclopentadienyl carbonates in a one-pot, two-step process, this chemistry enables expedient access to synthetically versatile alpha ' -chiral cyclopentenones with excellent enantiomeric excesses from easily accessible enynyl carbonate substrates.