Perfluoroalkylations, tetrabutylammonium fluoride

Alkyl halides, including bcnzylic and allylic halides, do not react with trimethyl(trifluoro-methyl)silane. even with molar amounts of tetrabutylammonium fluoride. A convenient method has been developed for the perfluoroalkylation of organic (aryl, vinyl, benzyl and allyl) halides, e.g. formation of 1. using a mixture of trialky (perfluoroalkyl)silane/potas-sium fluoride/copper in dimethylformamide. Under these conditions perfluoroalkylcopper RpCu reagents are produced in situ. 

Trimethyl(trifluoroniethyl)silane reacts with dimethyl sulfoxide in the presence of catalytic amounts of tetrabutylammonium fluoride to give the stable (perfluoroalkyl)siloxy-/4-sulfane 30, containing C — S and S O bonds.91... 

When activated by anionic catalysts [potassium fluoride, cesium fluoride, tetraalkylammonium fluorides, tris(dimethylamino)sulfonium difluorotrimethylsilicate, phosphazenium, hexa-methylpiperidinium and cobaltoccnium fluorides, tetrabutylammonium difluoroftriphenyl-silyl)silicatc. the complex tetrakis(dimethylamino)ethene/perfluoropropene, ammonium (and phosphonium) perfluorocyclobutane ylides], trimethyl(perfluoroalkyl)silanes will generate C-Rf bonds from carbon-halogen bonds. 

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