Eco‐Friendly and Additive‐Free Synthesis of CP Bonds: Synergistic Catalysis by a Polyoxovanadate‐Based Cu–Organic Framework Using Molecular Oxygen

Development of environmentally benign methods for CP bond formation is of great significance due to the extensive applications of organophosphorus compounds in pharmaceuticals and agrochemicals. Herein, we report a polyoxovanadate‐based Cu–organic framework, [Cu 3 (pty) 2 ][V 8 O 23 ]·H 2 O ( Cu‐POV , pty = 4′‐(pyridin‐4‐yl)‐2,2′:6′,2″‐terpyridine), for catalyzing the cross‐dehydrogenative coupling of N‐aryl tetrahydroisoquinolines with diarylphosphine oxides to form CP bonds using molecular oxygen (O 2 ) as an oxidant in green ethanol medium. The outstanding efficiency of Cu‐POV stems from a synergistic mechanism involving its structural Cu II and V V centers: the two activate the N‐aryl tetrahydroisoquinolines through single‐electron transfer and subsequently react with O 2 to generate the key superoxide radical species. The catalyst can be recycled at least six times without compromising performance, and applied in gram‐scale reaction with a turnover number of 2025.