"Breaking Carbon-Fluorine Bonds with Main Group Reagents"

Fluorocarbons surround us in modern life. These synthetic molecules find applications as refrigerants, aerosols and materials in homeware and electronic devices. The fluorocarbons market is expanding, and increasingly sophisticated methods are being developed to install fluorine into organic molecules. In contrast, the majority of natural fluorine containing substance are inorganic fluorides e.g cryolite [Na₃AlF₆] and fluorite [CaF₂]. There is a clear need to develop methods to recycle and reuse fluorine containing organics. This requires new types of chemical transformation to be developed that break strong C–F bonds.

In this lecture, I will describe our recent advances using main group reagents based on aluminium and magnesium to break strong carbon–fluorine bonds of fluoroarenes, fluoroalkenes and fluoroalkanes. These reactions result in the formation of reactive organometallics that can be applied in synthesis. Aspects of the mechanisms of these new reactions have been investigated by a combination of kinetics and DFT calculations.^[1-5]

References

[1]. G. Coates, B. J. Ward, C. Bakewell, A. J. P. White, M. R. Crimmin, Chem. Eur. J. 2018, accepted for publication. DOI: 10.1002/chem.201804580

[2]. C. Bakewell, A. J. P. White, and M. R. Crimmin Angew. Chem., Int. Ed. 2018, 57, 6638. DOI:10.1002/anie.201802321

[3]. C. Bakewell, B. J. Ward, A. J. P. White, M. R. Crimmin Chem. Sci. 2018, 9, 2348. DOI:10.1039/C7SC05059C

[4]. C. Bakewell, A. J. P. White, M. R. Crimmin, J. Am. Chem. Soc. 2016, 138, 12763 doi.org/10.1021/jacs.6b08104

[5]. M. R. Crimmin, M. J. Butler, A. J. P. White Chem. Commun. 2015, 51, 15994 DOI: 10.1039/c5cc07140b