Modular Access to Fluorinated Quaternary Stereocenters via Palladium/Lewis Base Synergistic Catalysis

Abstract The stereocontrolled construction of fluorinated quaternary stereocenters in acyclic systems remains a significant synthetic challenge. We report a synergistic palladium/Lewis base catalytic platform that directly couples α‐fluoro‐α‐aryl acetates with allenes or 1,3‐dienes without directing groups. This strategy overcomes traditional limitations in fluoronucleophile activation and stereochemical control, enabling access to diverse acyclic fluorinated architectures. Key to success is the use of axial‐chiral Lewis bases, which work cooperatively with palladium catalysts to govern both enantioselectivity and diastereoselectivity. The method accommodates broad substrate scope, including aromatic, heterocyclic, and aliphatic systems, while demonstrating scalability and synthetic versatility through downstream transformations. This work not only bridges essential voids in fluorinated stereochemical space but also enhances the practical applications of synergistic catalyst systems.