A Domino Palladium-Catalyzed C–C and C–O Bonds Formation via Dual O–H Bond Activation: Synthesis of 6,6-Dialkyl-6H-benzo[c]chromenes

An efficient Pd-catalyzed domino reaction of α,α-dialkyl-(2-bromoaryl)methanols to 6,6-dialkyl-6H-benzo[c]chromenes is presented. Their formation can be explained via a five membered Pd(II)-cycle that efficiently involves a domino homocoupling with the second molecule, β-carbon cleavage, and finally intramolecular Buchwald–Hartwig cyclization. This domino process effectively involves breaking of five σ-bonds (2C–Br, 2O–H, and a C–C) and formation of two new σ-bonds (C–C and C–O). This mechanistic pathway is unprecedented and further illustrates the power of transition metal catalysis.