Highly Diastereoselective Palladium-Catalyzed Oxidative Carbocyclization of Enallenes Assisted by a Weakly Coordinating Hydroxyl Group.

Abstract

A highly diastereoselective palladium-catalyzed oxidative carbocyclization-borylation of enallenes assisted by a weakly coordinating hydroxyl group was developed. The reaction afforded functionalized cyclohexenol derivatives, in which the 1,3-relative stereochemistry is controlled (d.r. > 50:1). Other weakly coordinating oxygen-containing groups (ketone, alkoxide, acetate) also assisted the carbocyclization toward cyclohexenes. The reaction proceeds via a ligand exchange on Pd of the weakly coordinating group with a distant olefin group. The high diastereoselectivity of the hydroxyl-directed reaction could be rationalized by a face-selective coordination of the distant olefin. It was demonstrated that the primary coordination of the close-by oxygen-containing functionality was necessary for the reaction to occur and removal of this functionality shut down the reaction.