Enantioselective 1,4-Addition of Unmodified Ketone Catalyzed by a Bimetallic Zn−Zn-Linked−BINOL Complex

1,4-Addition (Michael addition) of 2-hydroxy-2'-methoxyacetophenone (2) to various alpha,beta-unsaturated ketones was efficiently promoted by a bimetallic Zn-Zn-linked-BINOL complex 3 with good yield (up to 90%) and excellent enantiomeric excess (up to 99% ee). The resulting 2-hydroxy-1,5-diketones were successfully converted to synthetically more versatile esters and amides. [reaction: see text]