Bi(CF3)3/Cu(OCOCH3)2 - A new system for the synthesis of 2-trifluoromethylcycloalkan-1-ones, trifluoromethylanilines and phenyl(trifluoromethyl)sulfane
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.
De novo Design of Organic Photocatalysts: Bithiophene Derivatives for the Visible-light Induced C?H Functionalization of Heteroarenes
Herein, we report the de novo synthesis and characterization of a series of substituted bithiophene derivatives as novel and inexpensive organic photocatalysts. DFT calculations were used to predict a priori their absorption spectra and redox potentials, which were then confirmed with empirical data. The photocatalytic activity of this novel class of organic photoredox catalyst was demonstrated in two visible-light mediated strategies for the C?H functionalization of heteroarenes. The implementation of these strategies in a continuous-flow photo-microreactor afforded moderate to excellent yields within few minutes of reaction time. Due to their straightforward synthesis, low cost and good photocatalytic properties we believe that the proposed bithiophene derivatives could be employed as a new class of organic photoredox catalysts. (Figure presented.).
Bottecchia, Cecilia,Martín, Raúl,Abdiaj, Irini,Crovini, Ettore,Alcazar, Jesús,Orduna, Jesús,Blesa, María Jesús,Carrillo, José R.,Prieto, Pilar,No?l, Timothy
supporting information
p. 945 - 950
(2019/01/25)
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
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.
Stahl, Timo,Klare, Hendrik F. T.,Oestreich, Martin
supporting information
p. 1248 - 1251
(2013/03/29)
TRIFLUOROMETHYLATION OF AROMATIC AMINO AND THIO COMPOUNDS BY BISTRIFLUOROMETHYL TELLURIDE
The reaction of aromatic and heterocyclic amines with (CF3)2Te gave the products from trifluoromethylation in the aromatic ring.The reaction with the corresponding thiols gave S-trifluoromethyl derivatives.
Naumann, D.,Pazenok, S. V.,Turra, V.
p. 128 - 130
(2007/10/02)
Reactions of Trifluoromethyl Bromide and Related Halides: Part 10. Perfluoroalkylation of Aromatic Compounds induced by Sulphur Dioxide Radical Anion Precursors
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.
Tordeux, Marc,Langlois, Bernard,Wakselman, Claude
p. 2293 - 2299
(2007/10/02)
More Articles about upstream products of 106877-26-3