1210-31-7Relevant academic research and scientific papers
Substitution of fluorine in M[C6F5BF3] with organolithium compounds: Distinctions between O- and N-nucleophiles
Shabalin, Anton Yu.,Adonin, Nicolay Yu.,Bardin, Vadim V.
, p. 703 - 713 (2017/06/21)
Borates M[C6F5BF3] (M = K, Li, Bu4N) react with organolithium compounds, RLi (R = Me, Bu, Ph), in 1,2-dimethoxyethane or diglyme to give M[4-RC6F4BF3] and M[2-RC6Fsub
Palladium-catalyzed coupling reaction of perfluoroarenes with diarylzinc compounds
Ohashi, Masato,Doi, Ryohei,Ogoshi, Sensuke
supporting information, p. 2040 - 2048 (2014/03/21)
This report describes the first Pd0-catalyzed cross-coupling of hexafluorobenzene (C6F6) with diarylzinc compounds to give a variety of pentafluorophenyl arenes. This reaction could be applied to other perfluoroarenes, such as octafluorotoluene, pentafluoropyridine, and perfluoronaphthalene, to give the corresponding polyfluorinated coupling products. The optimal ligand in this catalytic reaction was PCy3, and lithium iodide was indispensable as an additive for the coupling reaction. One of the roles of lithium iodide in this catalytic reaction was to promote the oxidative addition of one Ci￡F bond of C6F 6 to palladium. Stoichiometric reactions revealed that an expected oxidative-addition product, trans-[Pd(C6F5)I(PCy 3)2], generated from the reaction of [Pd(PCy 3)2] with C6F6 in the presence of lithium iodide, was not involved in the catalytic cycle. Instead, a transient three-coordinate, monophosphine-ligated species, [Pd(C6F 5)I(PCy3)], emerged as a potential intermediate in the catalytic cycle. Therefore, we isolated a novel PdII complex, [Pd(C6F5)I(PCy3)(py)], in which pyridine (py) acted as a labile ligand to generate the transient species. In fact, in the presence of lithium iodide, this PdII complex was found to react smoothly with diphenylzinc to give the desired pentafluorophenyl benzene, whereas the same reaction conducted in the absence of lithium iodide resulted in a decreased yield of pentafluorophenyl benzene, which indicated that the other role of lithium iodide was to enhance the reactivity of the organozinc species during the transmetalation step.
REACTION OF HEXAFLUOROBUTADIENE WITH PHENYLACETYLENE. II. TRANSFORMATIONS OF THE -CYCLOADDUCT
Kaz'mina, N. B.,Mysov, E. I.,Kurbakova, A. P.,Leites, L. A.
, p. 1505 - 1508 (2007/10/02)
The -cycloadduct of hexafluorobutadiene and phenylacetylene is defluorinated thermally with the formation of tetrafluorobiphenyl.Thermal aromatization in glass is accompanied by concurrent hydrolysis of the CF2 group and the formation of 1-phenyltetrafluoro-1,4-cyclohexadien-3-one.
Homolytic Reactions of Polyfluoroaromatic Compounds. Part 16. Competitive Phenylation of Polyfluorobenzenes
Allen, Kim J.,Bolton, Roger,Williams, Gareth H.
, p. 691 - 696 (2007/10/02)
Pairs of polyfluorobenzenes were allowed to compete for phenyl radicals generated by thermolysis of benzoyl peroxide at 80 deg C.From the relative yields of biaryl, and the yields of each biaryl formed upon arylation of each arene individually, the relative rates of attack of each site in each arene were deduced.Neither iron(III) benzoate nor trichloroacetic acid uniformly improved yields of biaryl, although in some cases the isomer distribution altered, when decomposition of benzoyl peroxide was carried out in the presence of such additives, to favour products of aryldehydrogenation or of aryldefluorination, respectively.Competition did not usually affect the distribution of attack of a particular arene, except when hexafluorobenzene was used, in which case greater selectivity of attack of the second arene occured.This suggested the formation of a 'stabilised' phenyl radical, and supported an earlier suggestion of species such as >; other evidence also supported the postulate.
