Regio- and Enantioselective Functionalization of Quinone Imine Ketals Enabled by Gold and CPA Relay Catalysis

A relay catalytic system that combines AuCl with a chiral phosphoric acid enables asymmetric annulation of racemic α -amino ynones with quinone imine ketals, furnishing fully substituted pyrrol-3(2H)-ones bearing quaternary stereocenters. The reaction shows high regio- and enantioselectivity, broad tolerance of α -amino ynones, and compatibility with selected QIK variants, affording products in up to 93% yield and 98% ee. Millimole-scale synthesis and transformations demonstrate its synthetic utility.