Free radical chemistry. Part 10. Addition of acyclic and cyclic alkanes to hexafluoropropene

Footsteps of a fluorine chemist

“…29) [40]. These partly fluorinated products can have advantages for making inert fluids because the system is stabilized for further fluorination (Figs.…”

Perfluoroalkylation

“…The ''inverse'' addition of nucleophilic alkyl radicals to electrophilic, highly fluorinated olefins was the subject of a detailed study by Chambers and Sandford's group [33]. Alkyl radicals can be generated directly from alkanes either with initiators (such as DBPO, dibenzoyl peroxide) or by γ-irradiation.…”

Nucleophilic Substitution and Claisen Rearrangement Reactions of Model Fluoroalkenes of General Structure R−CFCF−CF3

“…Subsequent dehydrofluorination of the polyfluoroalkylated adducts 1 were accomplished 7 stereospecifically using sodium or potassium tert-butoxide, giving ready access to a range of potentially synthetically versatile fluoroalkenes 2 of general formula R-CFdCF-CF 3 . (Scheme 1)…”

“…The use of the carbon−hydrogen bond as a functional group in reactions between carbon-centered radicals, generated by carbon−hydrogen bond homolysis, with various fluoroalkenes has been developed considerably in these laboratories In particular, reactions of various alkane, alcohol, and ether − substrates, initiated by either gamma rays or peroxides, with industrially available hexafluoropropene, are very efficient processes, and a range of polyfluorinated products have been synthesized on a preparatively useful scale (Scheme ). It is perhaps worth reemphasizing here that no highly toxic tin derivatives (e.g., Bu 3 SnH) are used as initiators, and so all these processes are appropriate for scale-up.…”