Platinum-Catalyzed C-F Bond Reconstruction via the Multi-unit Insertion for Remote Fluorine Migration
1Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, 21 Gehu Road, Changzhou 213164, China.
Journal of the American Chemical Society
|June 30, 2025
Summary
Researchers developed a new platinum-catalyzed method for remote C-F bond formation. This strategy uses allylic gem-difluorides and N-heterocycles to precisely place fluorine atoms up to 19 bonds away in organic molecules.
Area of Science:
- Organic Chemistry
- Catalysis
- Fluorine Chemistry
Background:
- Precise control over fluorine atom placement in organic synthesis is a significant challenge.
- Existing methods often lack the ability for remote functionalization.
Purpose of the Study:
- To develop a novel strategy for remote C-F bond reconstruction.
- To enable intramolecular fluorine delivery over extended molecular distances.
Main Methods:
- Platinum-catalyzed multiunit insertion using allylic gem-difluorides and N-heterocycles.
- Investigation of a Pt-F shuttle mechanism involving nucleophilic insertions and ligand exchanges.
- Systematic studies on substrate stoichiometry and mechanistic investigations.
Main Results:
- Successful intramolecular delivery of fluorine over distances up to 19 bonds.
- High regioselectivity and atom economy in the C-F bond formation.
- Demonstration that coordinated Pt-F species, not free fluoride, mediate selective C-F bond formation.
Conclusions:
- Established a programmable platform for long-range fluorine transfer in catalysis.
- Developed a blueprint for remote C-F bond editing.
- Highlighted broad implications for molecular design, drug discovery, and fluorine-based materials.
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