Ru(II)-Catalyzed Difunctional Pyridyloxy-Directed Regio- and Stereospecific Addition of Carboxylic Acids to Internal Alkynes

A highly efficient Ru­(II)-catalyzed regio- and stereospecific hydro-oxycarbonylation of unsymmetrical internal alkynes bearing a difunctional 2-pyridyloxy directing group with carboxylic acids has been developed, which provides allylic (Z)-enol esters in good to excellent yields with a broad substrate scope under mild conditions. The difunctional directing group can be diversely derivatized, particularly undergoing allylic substitution with various nucleophiles to afford β-functionalized (Z)-enol esters without directing groups.