106877-26-3Relevant articles and documents
Bi(CF3)3/Cu(OCOCH3)2 - A new system for the synthesis of 2-trifluoromethylcycloalkan-1-ones, trifluoromethylanilines and phenyl(trifluoromethyl)sulfane
Kirij,Pasenok,Yagupolskii,Tyrra,Naumann
, p. 217 - 221 (2000)
Bi(CF3)3 reacts in the presence of equimolar amounts of Cu(OCOCH3)2 and 1-morpholinocyclopentene to give 1-morpholino-2-trifluoromethylcyclopentene in 83% yield. This compound as well as intermediately formed 1-morpholino-2-trifluoromethylcyclohexene can easily be converted into the corresponding cycloketones (78 and 41% yield) using the Swarts procedure. In absence of a copper(II) source, no reactions were observed. The reaction of the system Bi(CF3)3/Cu(OCOCH3)2 with N,N-diethylaniline gave an 1.7: 1 isomer mixture of 2-trifluoromethyl and 4-trifluormethyl-N,N-diethylanilines in 48% yield. With tetrabutylammonium thiophenolate, mixtures of phenyl(trifluoromethyl)sulfane and diphenyldisulfane were obtained. Mechanisms are discussed.
C(sp3)-F bond activation of CF3-substituted anilines with catalytically generated silicon cations: Spectroscopic evidence for a hydride-bridged Ru-S dimer in the catalytic cycle
Stahl, Timo,Klare, Hendrik F. T.,Oestreich, Martin
supporting information, p. 1248 - 1251 (2013/03/29)
Heterolytic splitting of the Si-H bond mediated by a Ru-S bond forms a sulfur-stabilized silicon cation that is sufficiently electrophilic to abstract fluoride from CF3 groups attached to selected anilines. The ability of the Ru-H complex, generated in the cooperative activation step, to intramolecularly transfer its hydride to the intermediate carbenium ion (stabilized in the form of a cationic thioether complex) is markedly dependent on the electronic nature of its phosphine ligand. An electron-deficient phosphine thwarts the reduction step but, based on the Ru-S catalyst, half of an equivalent of an added alkoxide not only facilitates but also accelerates the catalysis. The intriguing effect is rationalized by the formation of a hydride-bridged Ru-S dimer that was detected by 1H NMR spectroscopy. A refined catalytic cycle is proposed.
Reactions of Trifluoromethyl Bromide and Related Halides: Part 10. Perfluoroalkylation of Aromatic Compounds induced by Sulphur Dioxide Radical Anion Precursors
Tordeux, Marc,Langlois, Bernard,Wakselman, Claude
, p. 2293 - 2299 (2007/10/02)
Perfluoroalkylation of electron-rich aromatic compounds with trifluoromethyl bromide, or long-chain perfluoroalkyl iodides, was performed in the presence of sodium dithionite or zinc-sulphur dioxide.This alkylation occurred at the ortho and para positions relative to the amino or hydroxy substitutent.Pyrroles were perfluoroalkylated regioselectively at the 2-position.This alkylation was interpreted as a radical aromatic substitution; the formation of the perfluoroalkyl radical can be induced by a single-electron transfer from sulphur dioxide radical anion to the perfluoroalkyl halide.
