Trifunctional zirconium catalysis-enabled triple modular synthesis

While zirconium catalysis has been predominantly confined to Lewis acid and redox applications in homogeneous synthesis, its potential in photocatalysis—particularly in C–H activation—remains largely unexplored. Here, with the demonstration of photoinduced inner-sphere α-homolysis (ligand-to-metal charge transfer) in zirconium catalysis, we report a trifunctional zirconium catalytic system synergistically integrating photochemical, Lewis acid and redox catalysis for triple modular synthesis from alkanes, aldehydes and nitriles, rendering structurally diverse benzylamines (up to 98% yield) and their deuterated analogues under mild conditions. Mechanistic studies validate a multifunctional catalytic cycle combining ligand-to-metal charge transfer-initiated radical chemistry with a ZrIV-mediated carbocation pathway. The protocol’s synthetic power is showcased through late-stage diversification of bioactive compounds, streamlined drug analogue synthesis, direct valorization of gaseous alkanes and gram-scale production with 100% atom economy. Zirconium catalysis has remained largely confined to Lewis acid and redox chemistry, with only isolated examples of photocatalytic C–H activation. Now trifunctional zirconium catalysis enables modular benzylamine synthesis from alkanes, aldehydes and nitriles by integrating photochemical, redox and Lewis acid reactivity.