A practical and efficient method for selective intramolecular radical trifluoromethylacylation and -arylation of alkenes with inexpensive CF3SO2Na and K2S2O8 in aqueous media has been developed, respectively, affording the highly chemoselective synthesis of CF3-functionalized chroman-4-ones and chromanes in satisfactory yields. Control experiments and DFT calculations indicate that the CF3SO2Na/K2S2O8 system is capable of trifluoromethylating the substrate of alkenes without a transition metal catalyst and the oxidation of CF3SO2Na to ·CF3 by K2S2O8 is involved in the rate-determining step.

By altering the amount of Selectfluor, the highly selective mono-and difluorination of 1,3-dicarbonyl compounds has been achieved, affording a variety of 2-fluoro-and 2,2-difluoro-1,3-dicarbonyl compounds in good to excellent yields. The reaction can be readily performed in aqueous media without any catalyst and base, which features practical and convenient fluorination. Importantly, a gram-scale reaction, transformation of 2-fluoro-1,3-diphenylpropane-1,3-dione to 4-fluoro-1,3,5-triphenyl-1H-pyrazole, and chlorination and bromination of 1,3-dicarbonyl compounds are realized to further exhibit its synthetic utility.

By employing tert-butyl nitrite as both nitrogen source and oxidant, the trifluoromethyloximation of alkenes proceeds smoothly in afree-radical process. The developed difunctionalization reaction enables practical and efficient synthesis of a wide range of a-CF 3 ketoximes in moderate yields with excellent regioselectivity.T hism ethod features the use of readily availablea nd stable alkenes as substrates and inexpensive CF 3 SO 2 Na as aC F 3 reagent, no involvement of transition metals or externalo xidant, and room-temperature conditions. Moreover,ascale-upo ft he reaction, furthert ransformation of the products into variousv aluableC F 3 -containing compounds, and removal of the trifluoromethylg roup are readily achieved.

Herein, we have reported an efficient and green paired electrolysis strategy for decarboxylative coupling of alkenyl acids with diazo compounds, providing a broad range of β,γ-alkenyl esters and amides.