- New Electrophilic Trifluoromethylating Agents
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Synthetic routes to S-(trifluoromethyl)phenyl-4-fluorophenylsulfonium triflate (8), S-(trifluoromethyl)phenyl-2,4-difluorophenylsulfonium triflate (9), S-(trifluoromethyl)phenyl-3-nitrophenylsulfonium triflate (10), and S-(trifluoromethyl)-4-fluorophenyl-3-nitrophenylsulfonium triflate (11) are described. They are stable molecules and conveniently prepared by treating phenyl trifluoromethyl sulfoxide with benzene and its derivatives. These novel electrophilic trifluoromethylating agents react under mild conditions with a variety of aromatic rings (p-hydroquinone, pyrrole, and aniline) to give trifluoromethylated compounds (2-trifluoromethyl-p-hydroquinone, 2-trifluoromethylpyrrole, 2-trifluoromethylaniline, and 4-trifluoromethylaniline) in moderate to high yields. The electrophilic trifluoromethylating potential can be altered by placing electron-withdrawing substituents on the benzene rings.
- Yang, Jing-Jing,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
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- Straightforward one-pot synthesis of trifluoromethyl sulfonium salts
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(Chemical Equation Presented) Mix and wait: Trifluoromethyl sulfonium salts that are able to react as reagents in the trifluoromethylation of various nucleophiles are formed in a multicomponent reaction. The desired electrophilic reagents are prepared fro
- Magnier, Emmanuel,Blazejewski, Jean-Claude,Tordeux, Marc,Wakselman, Claude
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- Visible-Light Photocatalytic Tri- A nd Difluoroalkylation Cyclizations: Access to a Series of Indole[2,1- A[isoquinoline Derivatives in Continuous Flow
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A process for achieving photocatalyzed tri- A nd difluoromethylation/cyclizations for constructing a series of tri-or difluoromethylated indole[2,1-a]isoquinoline derivatives is described. This protocol utilized an inexpensive organic photoredox catalyst and provided good yields. Moreover, the combination of continuous flow and photochemistry, designed to provide researchers with a unique green process, was also shown to be key to allowing the reaction to proceed (product yield of 83% in flow vs 0% in batch).
- Yuan, Xin,Duan, Xiu,Cui, Yu-Sheng,Sun, Qi,Qin, Long-Zhou,Zhang, Xin-Peng,Liu, Jie,Wu, Meng-Yu,Qiu, Jiang-Kai,Guo, Kai
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supporting information
p. 1950 - 1954
(2021/04/05)
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- Cu-Mediated Trifluoromethylation of Aromatic α-Diazo Esters with the Yagupolskii–Umemoto Reagent
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Reductive trifluoromethylation of aromatic α-diazo esters at room temperature with the Yagupolskii–Umemoto reagent {[Ph2SCF3][OTf]; (2a)} in DMF in the presence of excess CuCl gave a variety of α-trifluoromethyl arylacetates in up to
- Hu, Xiao-Qian,Han, Jia-Bin,Zhang, Cheng-Pan
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supporting information
p. 324 - 331
(2017/01/24)
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- Palladium-Catalyzed Arylation of Arylboronic Acids with Yagupolskii-Umemoto Reagents
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A Pd-catalyzed Suzuki cross-coupling of arylboronic acids with Yagupolskii-Umemoto reagents was explored. In contrary to trifluoromethylations, the Pd-catalyzed reaction of R-B(OH)2 and [Ar2SCF3]+[OTf]- provided the arylation products (R-Ar) in good to high yields. The reaction confirms that the S-Ar bonds of [Ar2SCF3]+[OTf]- can be readily cleaved in the presence of Pd complexes. The relatively electron-poor aryl groups of asymmetric [Ar1Ar2SCF3]+[OTf]- salts are more favorably transferred compared to the electron-rich ones. This reaction represents the first report of utilization of [Ar2SCF3]+[OTf]- as arylation reagents in organic synthesis.
- Wang, Shi-Meng,Wang, Xiao-Yan,Qin, Hua-Li,Zhang, Cheng-Pan
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supporting information
p. 6542 - 6546
(2016/05/02)
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- PENTAFLUOROSULFANYL PHTHALOCYANINE DERIVATIVES AND INTERMEDIATES THEREOF
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Provided is a phthalocyanine derivative of the following general formula (1) which has superior solubility in organic solvents: General formula (1): (wherein M is a hydrogen atom, a metal element, a metalloid element, a metal oxide, a metalloid oxide, a m
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Paragraph 0102-0104
(2015/12/07)
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- Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes
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A regio- and stereoselective synthesis of trifluoromethylated alkenes bearing four different substituents has been developed. Stereocontrolled sulfonyloxytrifluoromethylation of unsymmetric internal alkynes with an electrophilic CF3 reagent, namely the triflate salt of the Yagupol'skii-Umemoto reagent, in the presence of an Ir photoredox catalyst under visible-light irradiation afforded trifluoromethylalkenyl triflates with well-predictable stereochemistry resulting from anti addition of the trifluoromethyl and triflate groups. Subsequent palladium-catalyzed cross-couplings led to tetrasubstituted trifluoromethylated alkenes in a highly stereoselective manner. The present method is the first example of a facile one-pot synthesis of tetrasubstituted trifluoromethylated alkenes from simple alkynes.
- Tomita, Ren,Koike, Takashi,Akita, Munetaka
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supporting information
p. 12923 - 12927
(2015/11/02)
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- Copper-mediated trifluoromethylation of heteroaromatic compounds by trifluoromethyl sulfonium salts
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Copper is king! A convenient method for the synthesis of trifluoromethylated heteroaromatic compounds under mild conditions has been developed based on the observation that 1 can be reduced by certain metals (see scheme). Substrate 1 is assumed to be reduced by copper via a single-electron transfer mechanism, and CuCF3 is the most probable intermediate in this reaction. DMF=N,N-dimethylformamide, Tf=triflate.
- Zhang, Cheng-Pan,Wang, Zong-Ling,Chen, Qing-Yun,Zhang, Chun-Tao,Gu, Yu-Cheng,Xiao, Ji-Chang
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supporting information; experimental part
p. 1896 - 1900
(2011/04/16)
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- Generation of the CF3 radical from trifluoromethylsulfonium triflate and its trifluoromethylation of styrenes
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The CF3 radical was generated from the reaction of S-(trifluoromethyl)diphenylsulfonium triflate with Na2S 2O4 or HOCH2SO2Na under suitable conditions without further reduction. Based on this, a method for the synthesis of α-trifluoromethylated ketones has been successfully developed.
- Zhang, Cheng-Pan,Wang, Zong-Ling,Chen, Qing-Yun,Zhang, Chun-Tao,Gu, Yu-Cheng,Xiao, Ji-Chang
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supporting information; experimental part
p. 6632 - 6634
(2011/06/27)
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- Benchmark and Solvent-Free preparation of sulfonium salt based electrophilic trifluoromethylating reagents
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Here we describe work devoted to the one-pot preparation of electrophilic trifluoromethylating reagents. The first part describes a reappraisal of our earlier experimental conditions and leads to an improved protocol that avoids the use of solvent: and allows better yields. The second part carefully studies the behavior of biaryl substrates, whose structures can drive the reaction through the formation of original noncyclic or tricyclic dibenzothiophenium salts. New compounds were tested, in a standard reaction with aniline, for their trifluoromethylating power and revealed equivalent or improved reactivity relative to that of existing reagents. Furthermore, contrary to common knowledge, the presence of electron-donating methyl groups gave reagents with very high activity. Wiley-VCH Verlag GmbH & Co, KGaA.
- Mace, Yohan,Raymondeau, Benoit,Pradet, Charlotte,Blazejewski, Jean-Claude,Magnier, Emmanuel
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scheme or table
p. 1390 - 1397
(2009/08/07)
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- Method for condensation of aromatic derivative(s) and a sulphinic derivative
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The invention concerns a method for the condensation of aromatic derivative(s) or a sulphinic derivative by a perhalogenated, advantageously perfluorinated, carbon atom. Said method is characterized in that it consists in subjecting said sulphinic derivat
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- Power-variable electrophilic trifluoromethylating agents. S-, Se-, and Te-(trifluoromethyl)dibenzothio-, -seleno-, and -tellurophenium salt system
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S-, Se-, and Te-trifluoromethylated dibenzoheterocyclic onium salts, their derivatives, and related salts were synthesized by the direct fluorination of a mixture of 2-[(trifluoromethyl)thio- or seleno]biphenyls and triflic acid (TfOH) or HBF4 etherate, by treatment of the corresponding sulfoxides and selenoxides with Tf2O, by a new type of tellurium activation of 2-[(trifluoromethyl)telluro]biphenyl with Tf2O and (CH3)2SO, or by derivation from the onium salts obtained. Examination of reactivity indicated the trifluoromethyl heterocyclic salts to be greatly reactive compared to nonheterocyclic salts and indicated that this heterocyclic salt system serves as a source of widely applicable trifluoromethylating agents. Their capacity to function as such varied remarkably and increased in the order of Te 2 2. For mixed heterocyclic salts, the orders differed, apparently being determined by the electron deficiency of the CF3 group due to the electron-withdrawing or -donating effects of chalcogens and ring substituents, rather than the inherent nature of the chalcogens. Because of this variation, it was possible to trifluoromethylate a wide range of nucleophilic substrates differing in reactivity: carbanions, activated aromatics, heteroaromatics, enol silyl ethers, enamines, phosphines, thiolate anions, and iodide anions. The reaction mechanism is discussed, and a bimolecular ionic substitution mechanism competing with a free CF3 radical chain mechanism is proposed. Thus, a new field, electrophilic trifluoromethylation, has been established by the present study.
- Umemoto, Teruo,Ishihara, Sumi
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p. 2156 - 2164
(2007/10/02)
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