- Structure and Reactivity of N-Heterocyclic Alkynyl Hypervalent Iodine Reagents
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Ethynylbenziodoxol(on)e (EBX) cyclic hypervalent iodine reagents have become popular reagents for the alkynylation of radicals and nucleophiles, but only offer limited possibilities for further structure and reactivity fine-tuning. Herein, the synthesis o
- Le Du, Eliott,Duhail, Thibaut,Wodrich, Matthew D.,Scopelliti, Rosario,Fadaei-Tirani, Farzaneh,Anselmi, Elsa,Magnier, Emmanuel,Waser, Jerome
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supporting information
p. 10979 - 10986
(2021/06/08)
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- Aryl Fluoroalkyl Sulfoxides: Optical Stability and pKa Measurement
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The enantiomeric separation of aryl trifluoromethyl and difluoromethyl sulfoxides was realized via chiral chromatography. The configurational stability of each set of enantiomers was then studied by thermal enantiomerization. The ΔG≠ values obt
- Messara, Amélia,Vanthuyne, Nicolas,Diter, Patrick,Elhabiri, Mourad,Panossian, Armen,Hanquet, Gilles,Magnier, Emmanuel,Leroux, Frédéric R.
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supporting information
p. 5019 - 5026
(2021/08/13)
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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Optimization and Gram-Scale Preparation of S-Trifluoromethyl Sulfoximines and Sulfilimino Iminiums, Powerful Reagents for the Late Stage Introduction of the CF3 Group
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S-Trifluoromethyl sulfoximines and S-trifluoromethyl sulfilimino iminiums are important reagents for the electrophilic or radical late-stage introduction of the CF3 group. We disclose in this article a reappraisal of our previous methodologies
- Barthelemy, Anne-Laure,Certal, Victor,Dagousset, Guillaume,Anselmi, Elsa,Bertin, Luc,Fabien, Laurence,Salgues, Bruno,Courtes, Philippe,Poma, Christian,El-Ahmad, Youssef,Magnier, Emmanuel
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p. 704 - 712
(2019/11/19)
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- One pot synthesis of trifluoromethyl aryl sulfoxides by trifluoromethylthiolation of arenes and subsequent oxidation with hydrogen peroxide
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Hydrogen peroxide was used for oxidation of various aryl trifluoromethyl sulfides. Trifluoroacetic acid was used as an activating solvent that enables non-catalyzed oxidation and increases selectivity for sulfoxide formation. As shown by oxidation of thianthrene TFA enhances electrophilic character of the oxidant and further oxidation of sulfoxide group is blocked. We have joined trifluoromethylthiolation of arenes using a modified Billard reagent (p-ClPhNHSCF3) with oxidation of aryl trifluoromethyl sulfides using 1.2 equiv. of 30% aqueous hydrogen peroxide and this one-pot process has superior yields than would have been obtained in a two step process.
- Horvat, Monika,Iskra, Jernej,Jereb, Marjan,Kodri?, Gregor
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p. 34534 - 34540
(2020/10/12)
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- General, practical and selective oxidation protocol for CF3s into CF3S(O) group
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A simple and efficient protocol for the oxidation of trifluoromethyl, mono- and difluoromethyl sulfides to the corresponding sulfoxides without over-oxidation to sulfones, using TFPAA prepared in situ from trifluoroacetic acid and 15% H2O2 aqueous solution was developed. The methodology is suitable for a wide range of aromatic and aliphatic substrates in milligram and multigram scales.
- Sokolenko, Liubov V.,Orlova, Raisa K.,Filatov, Andrey A.,Yagupolskii, Yurii L.,Magnier, Emmanuel,Pégot, Bruce,Diter, Patrick
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- Metal- and additive-free oxygen-atom transfer reaction: an efficient and chemoselective oxidation of sulfides to sulfoxides with cyclic diacyl peroxides
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Metal- and additive-free oxidation of a series of sulfides/thioketones has been achieved using cyclic diacyl peroxides as mild oxygen sources. This protocol features simple manipulation, high chemo- and diastereoselectivity, and a broad substrate scope (up to 42 examples), tolerates many common functional groups, and is scalable and applicable to the late-stage sulfoxidation strategy. A preliminary mechanistic study by quantum mechanical calculations suggests that a single two-electron transfer process is energetically more favorable, and indicates the reactivity of cyclic diacyl peroxides distinct from conventional acyclic acyl peroxides.
- Gan, Shaoyan,Yin, Junjie,Yao, Yuan,Liu, Yang,Chang, Denghu,Zhu, Dan,Shi, Lei
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supporting information
p. 2647 - 2654
(2017/04/03)
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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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- Br?nsted Acid-Mediated Hydrative Arylation of Unactivated Alkynes
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The Br?nsted acid-mediated reaction of unactivated alkynes with aryl sulfoxides leads to simultaneous hydration and intermolecular C-C bond formation. This solvent- A nd metal-free transformation directly delivers α-arylated carbonyl compounds as the prod
- Kaiser, Daniel,Veiros, Luís F.,Maulide, Nuno
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supporting information
p. 4727 - 4732
(2016/04/05)
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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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- 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 0101
(2015/12/07)
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- Sulfoxide-to-sulfilimine conversions: Use of modified Burgess-type reagents
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Sulfoxides can directly be converted into N-cyanosulfilimines using a new Burgess-type reagent. By applying this strategy with a related reagent variant, synthetically valuable NH-sulfoximines have been prepared from sulfoxides via N-protected sulfilimines. The practical three-step reaction sequence is generally high yielding and applicable to a wide range of substrates. The sulfoxide-to-sulfilimine conversion can also be performed under solvent-reduced conditions in a ball mill. Copyright
- Hendriks, Christine M. M.,Lamers, Philip,Engel, Julien,Bolm, Carsten
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supporting information
p. 3363 - 3368
(2013/12/04)
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- Selective sulfoxidation of thioethers and thioaryl boranes with nitrate, promoted by a molybdenum-copper catalytic system
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The catalytic reduction of nitrate by molybdo-enzymes plays a central role in the global biological cycle of nitrogen. However, the use of nitrates as oxidants in synthetic organic chemistry is very limited and typically requires very strong acidic and other extreme reaction conditions. We have developed a highly chemoselective and efficient catalytic process for the sulfoxidation of thioethers and arylthioethers containing boronic acid or boronic ester functional groups, using nitrate salts as oxidants. This homogeneous catalytic reaction was carried out in acetonitrile, where the MoO2Cl 2(OPPh3)2 complex 1 or a mixture of complex 1 with Cu(NO3)2 were used as catalysts. We examined the reaction mechanism using 1H, 15N, and 31P NMR techniques and 18O-labeled sodium nitrate (NaN18O 3) and show that the thioethers are oxidized by nitrate, generating nitrite. Our work adds to the existing chemical transformations available for organoboron compounds, providing straightforward accessibility to a variety of new substrates that could be suitable for Suzuki cross-coupling chemistry.
- Marom, Hanit,Antonov, Svetlana,Popowski, Yanay,Gozin, Michael
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experimental part
p. 5240 - 5246
(2011/08/09)
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- Selective oxidation and chlorination of trifluoromethylsulfide using trichloroisocyanuric acid in ionic liquid
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A route to chemoselective oxidation and chlorination of aryltrifluoromethylsulfide using trichloroisocyanuric acid (TCCA) in ionic liquid, an efficiently O-methylation reaction and a reduction of nitro- to amido- in excellent yields have been developed.
- Tang, Ri-Yuan,Zhong, Ping,Lin, Qiu-Lian
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p. 636 - 640
(2008/01/06)
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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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p. 1279 - 1282
(2007/10/03)
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- Synthesis of Sulfoxides by the Hydrogen Peroxide Induced Oxidation of Sulfides Catalyzed by Iron Tetrakis(pentafluorophenyl)porphyrin: Scope and Chemoselectivity
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The oxidation of sulfides with H2O2 catalyzed by iron tetrakis(pentafluorophenyl)porphyrin in EtOH is an efficient and chemoselective process. With a catalyst concentration 0.03-0.09% of that of the substrate, sulfoxides are obtained with yields generally around 90-95% of isolated product. With vinyl and allyl sulfides, no epoxidation is observed. With a catalyst concentration between 0.09% and 0.25% of that of the substrate, sulfones are obtained in almost quantitative yield and with the same high chemoselectivity observed in the synthesis of sulfoxides.
- Baciocchi, Enrico,Gerini, Maria Francesca,Lapi, Andrea
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p. 3586 - 3589
(2007/10/03)
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- Trifluoromethylating reagents and synthesizing processes
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A family of electrophilic trifluoromethylating reagents which can be synthesized by comparatively simple, inexpensive routes, and for which the reactivity can be varied according to need. A composition of matter according to the first embodiment of the invention comprises a compound having the formula: in which A comprises H or F and B comprises F, SCF3, OCF3, OCHF2, S+(CF3)C6H5, NO2or an NO2substituent. In a second embodiment of the invention, a process for preparing a trifluoromethyl diphenylsulfonium triflate compound corresponding to the formula shown above comprises reacting phenyl trifluoromethyl sulfoxide or one of its derivatives with an aromatic compound in which A comprises H or F and B comprises H, F, SCF3, OCF3, OCHF2, S+(CF3)C6H5, NO2or an NO2substituent. In a third embodiment of the invention, a trifluoromethylation process comprises reacting a trifluoromethyl diphenylsulfonium triflate corresponding to the formula shown above with an electron rich substrate.
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- Cesium fluoride catalyzed trifluoromethylation of esters, aldehydes, and ketones with (trifluoromethyl)trimethylsilane
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The low reactivity of carboxylic esters toward (trifluoromethyl)trimethylsilane (TMS-CF3) was investigated. A universal cesium fluoride catalyzed procedure for nucleophilic trifluoromethylation was developed. At room temperature (25 °C, with catalytic amounts of cesium fluoride, carboxylic esters were found to react to give the silyl ether intermediates, which afforded the trifluoromethyl ketones after hydrolysis. Sulfonic, sulfinic, and selenic esters also show good reactivity, giving novel trifluoromethylated compounds. The trifluoromethylation method was also applied to aldehydes and ketones, which were transformed to trifluoromethyl silyl ether intermediates and afforded trifluoromethylated alcohols in excellent yields after acid hydrolysis. Ethylene glycol dimethyl ether was used as solvent for solid or high boiling substrates, and benzonitrile was used for the low boiling substrates.
- Singh, Rajendra P.,Cao, Ganfeng,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
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p. 2873 - 2876
(2007/10/03)
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- 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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p. 2656 - 2660
(2007/10/03)
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- Nucleophilic trifluoromethylation of organic substrates using (trifluoromethyl)trimethylsilane in the presence of a fluoride anion. II. A convenient route to aryltrifluoromethyl-sulfides, - sulfoxides and -sulfones
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Aryltrifluoromethyl-sulfides, -sulfoxides and -sulfones can be prepared by trifluoromethylation of the corresponding arylsulfenyl, -sulfinyl and -sulfonyl halides using (trifluoromethyl)trimethylsilane in the presence of fluoride sources, such as TASF . - Keywords: Nucleophilic trifluoromethylation; (Trifluoromethyl)trimethylsilane; Fluoride anion; Aryltrifluoromethylsulfides; Aryltrifluoromethylsulfoxides; Aryltrifluoromethylsulfones
- Movchun, Valeria N.,Kolomeitsev, Alexander A.,Yagupolskii, Yurii L.
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p. 255 - 258
(2007/10/02)
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