- Palladium-catalyzed base-free Suzuki-Miyaura coupling reactions of fluorinated alkenes and arenes via a palladium fluoride key intermediate
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A new strategy for C-C bond formation with organoboronates through C-F activation of fluorinated alkenes and arenes was developed. In this Pd-catalyzed Suzuki-Miyaura-type cross-coupling reaction, neither a base for enhancing the reactivity of the organoboron reagents nor a Lewis acid for promoting C-F bond activation was required. A fluoropalladium intermediate played an essential role in this reaction. In addition, a Ni(NHC) catalyst was efficient for C-C coupling through C-F bond activation of fluoroarenes. Pd0/PR 3 complexes promote C-C bond formation with organoboronates through C-F bond activation of fluorinated alkenes. Mechanistic studies show that a PdII fluoride intermediate plays an essential role in this base-free cross-coupling reaction. Moreover, a Ni(NHC) catalyst is efficient for C-C coupling through C-F bond cleavage of fluoroarenes. Copyright
- Ohashi, Masato,Saijo, Hiroki,Shibata, Mitsutoshi,Ogoshi, Sensuke
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supporting information
p. 443 - 447
(2013/02/26)
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- Coupling reactions of chlorofluoro and perfluoroalkyl iodides
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Coupling reactions of chlorofluoro- and perfluoroalkyl iodides R f-I with Rf = ClCF2CFCl-(CF2) 3CF2-, ClCF2CFClO(CF2) 3CF2-, ClCF2CFCl-, (CF3) 2CF- , (CF3)2CFCF2CF2- in the presence of a zinc/solvent system give dimers in good yields. Both homodimerizations (one iodide) and heterodimerizations (two different iodides) have been studied. The effect of temperature and solvent is shown. The zinc mediated dechlorination of vicinal chlorine atoms in the dimers afforded terminal alkenes and dienes.
- Wlassics, Ivan,Tortelli, Vito
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scheme or table
p. 1719 - 1728
(2009/06/05)
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- Thermolytic transformations of polyfluoroorganic compounds 30. Copyrolysis of α,α-dichlorooctafluoroethylbenzene with tetrafluoroethylene
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The reaction of α,α-dichlorooctafluorobenzene with tetrafluoroethylene as a source if difluorocarbene has been studied.The copyrolysis of these compounds gave not only the expected products, decafluoro-α-methylstyrene and α-chloroheptafluorostyrene, but also noticeable amounts of perfluoro-1-methylindan and perfluoro-7-methylbicyclonona-1,4,6-triene along with perfluoro-3-methylindene and octafluorostyrene.It has been suggested that indan and the triene are formed with the participation of the C6F5CClCF3 radical through sigmatropic shifts of fluorine atoms in the intermediate bicyclic compounds.The reaction of α,α-dichlorodecafluoropropylbenzene with tetrafluoroethylene afforded α-chloroheptafluorostyrene as the main product. - Key words: copyrolysis; decafluoro-α-methylstyrene, perfluoro-7-methylbicyclonona-1,4,6-triene; perfluoro-1-methylindan; polyfluoroalkylbenzyl radicals; sigmatropic shifts of fluorine atoms.
- Dvornikova, K. V.,Platonov, V. E.,Yakobson, G. G.
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p. 1690 - 1693
(2007/10/02)
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