BrettPhos Ligand Supported Palladium-Catalyzed CO Bond Formation through an Electronic Pathway of Reductive Elimination: Fluoroalkoxylation of Activated Aryl Halides

We report an unprecedented BrettPhos ligand supported Pd‐catalyzed CO bond‐forming reaction of activated aryl halides with primary fluoroalkyl alcohols. We demonstrate that the Phosphine ligand (BrettPhos) possesses the property of altering the mechanistic pathway of reductive elimination from nucleophile to nucleophile. The Pd/BrettPhos catalyst system facilitates the reductive elimination of the oxygen nucleophile through an electronic pathway. CO coupling: A BrettPhos ligand supported Pd‐catalyzed CO bond‐forming reaction of activated aryl halides with primary fluoroalkyl alcohols is reported. BrettPhos ligand (L1) can alter the mechanistic pathway of reductive elimination from nucleophile to nucleophile (see scheme; Rf=–(CF2)nCF3; R=electron‐releasing groups (ERGs) at o‐, m‐ and p‐positions, neutral, and electron‐withdrawing groups at o‐ and m‐positions; EWG=electron‐withdrawing group).