Metal–Organic Framework with Dual Active Sites in Engineered Mesopores for Bioinspired Synergistic Catalysis

Here we report the design of an enzyme-inspired metal–organic framework (MOF), 1 -OTf-Ir, by installing strong Lewis acid and photoredox sites in engineered mesopores. Al-MOF ( 1 ), with mixed 2,2′-bipyridyl-5,5-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands, was oxidized with ozone and then triflated to generate strongly Lewis acidic Al-OTf sites in the mesopores, followed by the installation of [Ir(ppy) 2 (dcbpy)] + (ppy = 2-phenylpyridine) sites to afford 1 -OTf-Ir with both Lewis acid and photoredox sites. 1 -OTf-Ir effectively catalyzed reductive cross-coupling of N -hydroxyphthalimide esters or aryl bromomethyl ketones with vinyl- or alkynyl-azaarenes to afford new azaarene derivatives. 1 -OTf-Ir enabled catalytic synthesis of anticholinergic drugs Pheniramine and Chlorpheniramine.