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Diversifying fluoroalkanes: light-driven fluoroalkyl transfer via vinylboronate esters.

Kaushik Chakrabarti1, Chandana Sunil1, Benjamin M Farris1

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A novel synthetic strategy enables the creation of tertiary difluoromethylene molecules using fluoroalkane precursors and vinyl-pinacol boronic ester reagents. This method offers a versatile, one-pot protocol tolerant to various functional groups and reaction conditions.

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Area of Science:

  • Organic Synthesis
  • Fluorine Chemistry
  • Radical Reactions

Background:

  • Tertiary difluoromethylene motifs are valuable in pharmaceuticals and materials science.
  • Existing synthetic methods often lack versatility or require stringent conditions.
  • Efficient and robust methods for introducing -CF2- groups are highly sought after.

Purpose of the Study:

  • To develop a new, versatile synthetic strategy for tertiary difluoromethylene-containing molecules.
  • To establish a one-pot protocol utilizing readily available fluoroalkanes and vinyl-pinacol boronic ester reagents.
  • To investigate the reaction mechanism and scope of the developed method.

Main Methods:

  • Photochemical conjugate radical addition of fluoroalkyl(vinyl)pinacol boronate esters.
  • One-pot synthesis employing fluoroalkane precursors (RCF2H) and vinyl-pinacol boronic ester (vinyl-BPin) reagents.
  • Experimental and theoretical mechanistic studies including radical initiation and ionic rearrangement.

Main Results:

  • Successful synthesis of tertiary difluoromethylene molecules from fluoroalkane precursors.
  • Demonstrated tolerance to oxygen and nitrogen heterocycles, and common functional groups.
  • Versatile application using HFC-23, HFC-32, and difluoromethyl heteroarenes as precursors.
  • Elucidation of a reaction mechanism involving radical initiation and a 1,2-boronate rearrangement.

Conclusions:

  • A new, efficient, and versatile synthetic strategy for tertiary difluoromethylene compounds has been established.
  • The developed one-pot protocol offers a practical approach using accessible starting materials and mild conditions.
  • The mechanistic insights provide a foundation for further development and application of this methodology.