Iron- and Organo-Catalyzed Borrowing Hydrogen for the Stereoselective Construction of Tetrahydropyrans.

Abstract

Stereocontrolled oxa-Michael additions are challenging, given the high reversibility of the process, which ultimately leads to racemization of the newly formed stereocenters. When iron-catalyzed borrowing hydrogen from allylic alcohols was combined with a stereocontrolled organocatalytic oxa-Michael addition, a wide array of chiral tetrahydropyrans were efficiently prepared. The reaction could be performed in a diastereoselective manner from pre-existing stereocenters or enantioselectively from achiral substrates. The key to success was the reactivity of the iron complex, which was selective for allylic alcohol dehydrogenation and irreversibly led the reaction to the final product.