Redox reactions perfluoroalkylation

Metal-assisted cycloaddition reactions involving meso-perfluoroalkylated porphyrinic templates define a versatile methodology for the syntheses of both cofacial porphyrin structures and facially-functionalized (porphinato)metal species [62], and corresponding compositions that offer new opportunities for development of small molecule redox catalysts [63, 64]. Scheme 21 shows the versatile metal-mediated [2+2+2] cycloaddition step for the isolation of meso-perfluoroalkyl cofacial porphyrins that results in the purified indane complexes in 10-12 % yields. These cofacial complexes are directly applicable to multi-electron redox reactions such as oxygen or nitrogen reduction and even hydrocarbon oxidation. 

Perfluoroalkyl iodides reacted with trialkylsilyl chloride in DMF in the presence of zinc followed by hydrolysis with acid to give perfluoroaldehydes in good yields [55]. Recently, Hu reported a new preparation of perfluoroalkyl aldehydes via reaction of perfluoroalkyl halides and DMF, initiated by redox... 

A bimetal redox couple, zinc/cobaloxime, promotes hydropcrfluoroalkylation of electron-deficient alkenes, such as acrylates, acrylonitrile and methyl vinyl ketone, by perfluoroalkyl iodides and bromides, hydrogen replacing iodine or bromine. A typical reaction is the formation of2. ... 

Analogous trans-a,dditions of perfluoroalkyl iodides to terminal or internal alkynes in the presence of sodium dithionite and mediated by ultrasonic irradiation or catalysed by triethylborane have been reported. 1,2-Dibromotetrafluoroethane reacts with terminal acetylenes in DMF in the presence of the redox system (NH4)2S208/HC02Na.2H20 to yield a mixture of mainly (E)- and some (Z)-olefins 237, the initial adducts having undergone reductive debromination under the reaction conditions... 

---