Platinum-Catalyzed C-F Bond Reconstruction via the Multi-unit Insertion for Remote Fluorine Migration.

Abstract

Precise control over fluorine positioning in organic molecules remains a long-standing challenge in synthetic chemistry. Here, we report a conceptually distinct strategy for remote C-F bond reconstruction via platinum-catalyzed multiunit insertion. This transformation exploits allylic gem-difluorides as modular fluorinated synthons and strained N-heterocycles as directional coupling partners, enabling the intramolecular delivery of fluorine over distances spanning up to 19 bonds. Central to this process is a Pt-F shuttle mechanism, wherein successive nucleophilic insertions and ligand exchanges guide fluoride relocation with high regioselectivity and atom economy. Systematic studies reveal that the extent of fluorine migration is governed by substrate stoichiometry, while mechanistic investigations confirm that selective C-F bond formation is mediated by coordinated Pt-F species, rather than by free fluoride anions. This work establishes a programmable platform for long-range fluorine transfer in catalysis, offering a blueprint for remote editing of C-F bonds with broad implications in molecular design, drug discovery, and fluorine-based materials.