Aerobic oxidative dimerization of hydroxystilbenoids is described. A Cr-salen complex catalyzed the dimerization of hydroxystilbenoids in 1,1,1,3,3,3-hexafluoroisopropanol to form compounds comprising a natural product-like scaffold (quadrangularin) or its precursor depending on the aromatic substituents. The addition of a catalytic amount of scandium triflate [Sc(OTf)3] to the reaction system altered the reaction outcome to give a different natural product-like compound, a pallidol-type dimer.