Re2O7 catalyzed tandem allylic alcohol isomerization/oxa-Michael addition reaction of cyclohexadienone was developed. The reaction features a regioselective and stereoselective isomerization of allylic alcohol and diastereoselective ring closure via oxa-Michael addition. This method also enabled construction of enantiopure bicyclic enones from substrates incorporated with chiral allylic alcohol via efficient chirality transfer.
