Abstract: A rapid and highly productive synthetic microwaveirradiationprotocol for transition-metal-catalyzed carbon–carboncoupling of a wide range of benzylic/allylic alcohols with b-diones,b-keto esters, and dialkyl malonates is reported. In a representativescreening of transition-metal catalysts, salts of Zn, Cu, Fe, Sc, Ru,Pt, Ta, and Mo were found to furnish the coupling products. In lightof the results obtained, among all of these catalysts copper(II) triflatewas found to be relatively more effective compared to othercatalysts even in the case of a less reactive benzyl alcohol or diester.Interestingly, these MW-irradiated reactions are performed in amore or less MW-transparent medium, such as toluene, having avery low tand, or under neat conditions.