Discovery of ammonium salts of alpha-fluoroarylated Meldrum's acid derivatives

Case ID:
2015-003

BACKGROUND

Meldrum’s acid is widely used as a building block in the synthesis of diverse organic compounds, including natural products and pharmaceuticals. Despite its broad utility, efficient and general methods for the direct mono-arylation of Meldrum’s acid remain limited. At the same time, there is a growing demand for partially fluorinated arenes in the pharmaceutical, agrochemical, and materials industries due to their valuable properties. Developing a strategy that couples the reactivity of Meldrum’s acid with perfluorinated or polyfluorinated aromatics would enable rapid and selective access to synthetically versatile, fluorinated building blocks with broad applicability.


SUMMARY OF TECHNOLOGY

Researchers at Oklahoma State University have developed a patented nucleophilic aromatic substitution method enabling highly selective mono-arylation of Meldrum’s acid (and analogs) with electron-deficient perfluoro- and polyfluoroarenes. The reaction proceeds rapidly under mild conditions using non-nucleophilic bases, such as DIPEA, in polar aprotic solvents, overcoming past limitations that often led to undesired diarylation. This technology also allows for the modular construction of fully substituted quaternary carbon centers through sequential alkylation and perfluoroarylation steps. The resulting α-arylated and fluorinated Meldrum’s acid derivatives serve as robust synthons for further chemical transformations, including photocatalytic hydrodefluorination, expanding the toolbox for accessing complex, fluorinated molecules without relying on expensive or toxic aryl-Pb(IV) or diaryliodonium salts.

POTENTIAL AREAS OF APPLICATION

  • Advanced Materials for Semiconductor Processing
  • High-Performance Lubricant Formulations; Machinery
  • Fluorinated Surfactants for Industrial Applications
  • Fine Chemical Manufacturing; Pharmaceuticals, Agrochemicals
  • Chemical Research & Development Servies; Innovative Chemical Compounds/Processes/Materials

MAIN ADVANTAGES

  • Highly Selective for Mono-Perfluoroarylation Over Diarylation
  • Rapid Reaction Times Under Mild Temperatures (20-80°C)
  • Use of Readily Available, Non-Toxic Reagents
  • Highly Stable, Low-Surface-Energy Compound

STAGE OF DEVELOPMENT

  • Working Model

 

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Patent Information:
For Information, Contact:
Russell Hopper
Sr. Licensing Associate
Oklahoma State University
russell.hopper@okstate.edu
Inventors:
Sameera Senaweera
Jimmie Weaver
Keywords:
Research Tools & Methods
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