Orthogonal One‐Pot Dual Catalysis Enabled by a Hybrid Chiral Diene/Phosphine Ligand

A hybrid chiral diene‐phosphine ligand ( L1 ) enables orthogonal one‐pot relay catalysis by integrating distinct metal‐coordination sites within a single molecular framework. The ligand combines a chiral diene with high affinity for rhodium and an electron‐rich biaryl phosphine selective for palladium, promoting tandem Rh‐catalyzed asymmetric arylation and Pd‐catalyzed cross‐coupling under one‐pot conditions. The catalytic system achieves up to 100% yield and 97.7:2.3 e.r . for aryl bromides, with a turnover number (TON) of 200 and turnover frequency (TOF) of 0.037 s −1 at low catalyst loadings. L1 outperforms analogous dual‐ligand systems, particularly in transformations involving less reactive aryl chlorides. Mechanistic analysis indicates that selective metal coordination governs both reactivity and selectivity: The diene unit promotes enantioinduction and transmetalation at rhodium, while the phosphine fragment facilitates oxidative addition and stabilizes reactive palladium intermediates. These results establish hybrid ligand design as a viable strategy for orchestrating orthogonal catalytic cycles in multifunctional systems.