- Recyclable alkylated Ru(bpy)32+ complex as a visible-light photoredox catalyst for perfluoroalkylation
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A recyclable Ruthenium tris [4,4′-bis (dinonylmethyl)-2,2′-bipyridine] (Ru[(DNM)2bpy]32+) photocatalyst (PC) was synthesized. Hexane-phase-selective solubility allowed its simple and efficient separation from reaction products via solvent extraction. The excellent catalytic activity and recoverability were demonstrated in batch and flow perfluoroalkylation reactions of coumarin under visible-light irradiation. High reaction rates and easy reusability of the catalyst make this approach attractive for large-scale applications.
- Zhang, Xiaodan,Li, Yaming,Hao, Xinyu,Jin, Kun,Zhang, Rong,Duan, Chunying
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Read Online
- 5-HT2A AGONISTS FOR USE IN TREATMENT OF DEPRESSION
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The present invention relates to agonists of the 5-HT2A serotonin receptors and their medical uses. In one aspect the invention relates to 5-HT2A agonists of formula (I). In second aspect, the invention relates to selective 5-HT2A agonists of formula (II). In another aspect, the invention relates to mixed 5-HT2A/5-HT2C agonists of formula (III). In yet another aspect, the invention relates to 5-HT2A agonists for use in the treatment of a depressive disorder, more particular a 5-HT2A agonist for the use in the treatment of treatment-resistant depression.
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Paragraph 0454
(2021/05/14)
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- Exploring the Structure and Performance of Cd–Chalcogenide Photocatalysts in Selective Trifluoromethylation
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The field of heterogeneous photoredox catalysis has grown substantially and impacted organic synthesis because of the affordability and reusability of catalysts. This study reports radical trifluoromethylation with Cd–chalcogenide semiconductors. Cd semiconductors, particularly CdSe, are readily available, commercial, visible-light-responsive, heterogeneous photocatalysts. The potential of readily available Cd semiconductors, particularly CdSe, is confirmed by their increased photocatalytic activity toward trifluoromethylation with various substrates, such as (hetero)arenes and vinylic amides/acids, via addition, cyclization, and decarboxylation under visible light. The economic significance of this strategy is also highlighted through the scalable synthesis of biologically active molecules followed by catalyst reuse. Moreover, these catalysts are relatively inexpensive compared with transition metal-based homogeneous photocatalysts, presently used in organic synthesis.
- Muralirajan, Krishnamoorthy,Kancherla, Rajesh,Bau, Jeremy A.,Taksande, Mayur Rahul,Qureshi, Muhammad,Takanabe, Kazuhiro,Rueping, Magnus
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p. 14772 - 14780
(2021/12/09)
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- Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High-Valent Nickel Complexes
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We describe a series of air-stable NiIII complexes supported by a simple, robust naphthyridine-based ligand. Access to the high-valent oxidation state is enabled by the CF3 ligands on the nickel, while the naphthyridine exhibits either a monodentate or bidentate coordination mode that depends on the oxidation state and sterics, and enables facile aerobic oxidation of NiII to NiIII. These NiIII complexes act as efficient catalysts for photoinduced C(sp2)?H bond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols. This blue LED light-mediated catalytic protocol proceeds via a radical pathway and demonstrates potential in the late-stage functionalization of drug analogs.
- Deolka, Shubham,Govindarajan, Ramadoss,Khaskin, Eugene,Fayzullin, Robert R.,Roy, Michael C.,Khusnutdinova, Julia R.
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supporting information
p. 24620 - 24629
(2021/10/08)
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- Regioselective C-H Trifluoromethylation of Aromatic Compounds by Inclusion in Cyclodextrins
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A regioselective radical C-H trifluoromethylation of aromatic compounds was developed using cyclodextrins (CDs) as additives. The C-H trifluoromethylation proceeded with high regioselectivity to afford the product in good yield, even on the gram scale. In the presence of CDs, some substrates underwent a single trifluoromethylation selectively, whereas mixtures of single- and double-trifluoromethylated products were formed in the absence of the CD. 1H NMR experiments indicated that the regioselectivity was controlled by the inclusion of a substrate inside the CD cavity.
- Lu, Xu,Kawazu, Ryohei,Song, Jizhou,Yoshigoe, Yusuke,Torigoe, Takeru,Kuninobu, Yoichiro
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supporting information
p. 4327 - 4331
(2021/05/26)
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- Solid-State Radical C?H Trifluoromethylation Reactions Using Ball Milling and Piezoelectric Materials
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The application of piezoelectricity for the generation of trifluoromethyl (CF3) radicals is reported together with the development of a method for the mechanochemical C?H trifluoromethylation of aromatic compounds. As compared to conventional solution-based approaches, this mechanoredox C?H trifluoromethylation enables cleaner and more sustainable access to a wide range of trifluoromethylated N-heterocycles and peptides, which are important structural motifs in modern drug discovery. This study thus represents an important milestone for future applications of mechanoredox systems to medicinal and pharmaceutical science.
- Ito, Hajime,Kubota, Koji,Lee, Joo Won,Pang, Yadong
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supporting information
p. 22570 - 22576
(2020/10/21)
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- Alternating current electrolysis for organic electrosynthesis: Trifluoromethylation of (hetero)arenes
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Paired electrolysis has a limited reaction scope for organic synthesis because it is often not compatible with reactions involving short-lived intermediates. We addressed this limitation using alternating current electrolysis (ACE). Using trifluoromethyla
- Rodrigo, Sachini,Um, Chanchamnan,Mixdorf, Jason C.,Gunasekera, Disni,Nguyen, Hien M.,Luo, Long
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supporting information
p. 6719 - 6723
(2020/07/30)
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- Electrophotocatalytic Undirected C?H Trifluoromethylations of (Het)Arenes
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Electrophotochemistry has enabled arene C?H trifluoromethylation with the Langlois reagent CF3SO2Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for the generation of the CF3 radical. The electrophotochemistry was carried out in an operationally simple manner, setting the stage for challenging C?H trifluoromethylations of unactivated arenes and heteroarenes. The robust nature of the electrophotochemical manifold was reflected by a wide scope, including electron-rich and electron-deficient benzenes, as well as naturally occurring heteroarenes. Electrophotochemical C?H trifluoromethylation was further achieved in flow with a modular electro-flow-cell equipped with an in-operando monitoring unit for on-line flow-NMR spectroscopy, providing support for the single electron transfer processes.
- Qiu, Youai,Scheremetjew, Alexej,Finger, Lars H.,Ackermann, Lutz
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supporting information
p. 3241 - 3246
(2020/02/27)
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- Nickel(IV)-Catalyzed C-H Trifluoromethylation of (Hetero)arenes
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This Article describes the development of a stable NiIV complex that mediates C(sp2)-H trifluoromethylation reactions. This reactivity is first demonstrated stoichiometrically and then successfully translated to a NiIV-catalyzed C-H trifluoromethylation of electron-rich arene and heteroarene substrates. Both experimental and computational mechanistic studies support a radical chain pathway involving NiIV, NiIII, and NiII intermediates.
- Meucci, Elizabeth A.,Nguyen, Shay N.,Camasso, Nicole M.,Chong, Eugene,Ariafard, Alireza,Canty, Allan J.,Sanford, Melanie S.
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supporting information
p. 12872 - 12879
(2019/08/26)
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- Cathodic C-H Trifluoromethylation of Arenes and Heteroarenes Enabled by an in Situ-Generated Triflyltriethylammonium Complex
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While several trifluoromethylation reactions involving the electrochemical generation of CF3 radicals via anodic oxidation have been reported, the alternative cathodic, reductive radical generation has remained elusive. Herein, the first cathodic trifluoromethylation of arenes and heteroarenes is reported. The method is based on the electrochemical reduction of an unstable triflyltriethylammonium complex generated in situ from inexpensive triflyl chloride and triethylamine, which produces CF3 radicals that are trapped by the arenes on the cathode surface.
- Cantillo, David,Jud, Wolfgang,Kappe, C. Oliver,Maljuric, Snjezana
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supporting information
(2019/10/08)
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- Metal- and oxidant-free photoinduced aromatic trifluoromethylation performed in aerated gel media: Determining the effects on yield and selectivity
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In this work we have investigated the potential benefits of using supramolecular gel networks as reaction media to carry out air-sensitive metal-free light-induced trifluoromethylation of six-membered (hetero)arenes under aerobic conditions. This reaction was performed at room temperature (RT) using sodium triflinate (CF3SO2Na, Langlois' reagent) as a source of radicals and diacetyl as electron donor. The effects of confinement in gel media, concentration of reactants, and type of light source on yield and product distribution were evaluated and compared to the results obtained in homogeneous solution. Four different low molecular weight (LMW) gelators were employed in this study. The results confirmed the blocking effect of the gel medium against reaction quenching by external oxygen, as well as a certain control on the kinetics and selectivity.
- Abramov, Alex,Vernickel, Hendrik,Saldías, César,Díaz, David Díaz
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- CATALYST-FREE AND REDOX-NEUTRAL INNATE TRIFLUOROMETHYLATION AND ALKYLATION OF (HETERO)AROMATICS ENABLED BY LIGHT
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The present disclosure relates to reagents and method for performing trifluoromethylation, difluoromethylation or alkylation of aromatic or heteroaromatic rings in a redox-neutral manner without any catalyst which are enabled by light. In addition, there are methods for synthesizing the starting reagents used in the trifluoromethylation, difluoromethylation or alkylation reactions.
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Page/Page column 16-18
(2019/04/26)
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- Aryl trifluoromethylation of the compound of preparation method and application
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The invention discloses a aryl trifluoromethylation of the compound of preparation method and application. The preparation method comprises: the illumination and under alkaline conditions, making compound A and trifluoromethyl reagent in organic solvent containing the catalyst in the reaction system, to obtain the aryl trifluoromethylation of composition; A of the compounds shown in the following formula: A, The compound of the structural formula A in R is alkyl, alkoxy, hydroxy, halogen, nitro, carboxyl in the one or more than two. Preparation method of this invention the reaction condition is simple, only requiring illumination of the reaction material, the effect of the catalyst and the alkaline condition, can obtain the aryl trifluoromethylation of composition, preparation process does not need ligand, without precursor compound, product without catalyst residue.
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Paragraph 0067; 0069; 0071; 0072
(2018/07/15)
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- N -Aryltrifluoromethanesulfonimides as new trifluoromethylating agents for the (photo)catalyst-free functionalization of (hetero)aromatics
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The photoinduced (by UV or sunlight) catalyst-free radical trifluoromethylation of (hetero)aromatics (up to 87% yield) has been successfully achieved by using N-aryltrifluoromethanesulfonimides as the trifluoromethylating agents. The process likewise occu
- Torti, Edoardo,Protti, Stefano,Fagnoni, Maurizio
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supporting information
p. 4144 - 4147
(2018/04/27)
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- Photoinduced Cobalt(III)?Trifluoromethyl Bond Activation Enables Arene C?H Trifluoromethylation
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Visible-light capture activates a thermodynamically inert CoIII?CF3 bond for direct C?H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by a redox-active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi-octahedral [(SOCO)CoIII(CF3)(MeCN)2] (2), but in non-coordinating solvents the complex is red, square pyramidal [(SOCO)CoIII(CF3)(MeCN)] (3). Both are thermally stable, and 2 is stable in light. But exposure of 3 to low-energy light results in facile homolysis of the CoIII?CF3 bond, releasing .CF3 radical, which is efficiently trapped by TEMPO. or (hetero)arenes. The homolytic aromatic substitution reactions do not require a sacrificial or substrate-derived oxidant because the CoII by-product of CoIII?CF3 homolysis produces H2. The photophysical properties of 2 and 3 provide a rationale for the disparate light stability.
- Harris, Caleb F.,Kuehner, Christopher S.,Bacsa, John,Soper, Jake D.
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supporting information
p. 1311 - 1315
(2018/01/27)
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- A Vitamin B12 derivative catalyzed electrochemical trifluoromethylation and perfluoroalkylation of arenes and heteroarenes in organic media
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The electrochemical trifluoromethylation and perfluoroalkylation of aromatic compounds mediated by a vitamin B12 derivative as a cobalt-based catalyst has been developed. The Co(i) species of a vitamin B12 derivative, prepared by con
- Hossain, Md. Jakir,Ono, Toshikazu,Wakiya, Kosuke,Hisaeda, Yoshio
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supporting information
p. 10878 - 10881
(2017/10/11)
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- Catalyst-Free and Redox-Neutral Innate Trifluoromethylation and Alkylation of Aromatics Enabled by Light
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The Minisci alkylation is useful to functionalize aromatics via alkyl radical addition. Current approaches to prepare alkyl radicals follow either oxidative or reductive pathways from various functional groups. Developing new strategy beyond these traditional methods remains elusive yet highly significant. In this article, we present a redox-neutral and catalyst-free protocol to engender alkyl radicals in the context of trifluoromethylation and general alkylation of arenes. This protocol, via the Norrish type I concept to produce alkyl radicals, accommodates various functional groups and delivers the product in good yields. This method identified a series of compounds as the trifluoromethylation and alkylation reagents assisted by light. It is expected that these compounds can find potential applications in other radical-involved reactions.
- Liu, Peng,Liu, Wenbo,Li, Chao-Jun
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supporting information
p. 14315 - 14321
(2017/10/17)
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- Sunlight decatungstate photoinduced trifluoromethylations of (hetero)aromatics and electron-poor olefins
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Tetrabutylammonium decatungstate has been exploited to photoinduce the trifluoromethylation of (hetero)aromatics and electron-poor olefins. The process made use of the cheap Langlois' reagent (CF3SO2Na) and occurred under sunlight irradiation in an acetonitrile/water mixture. The trifluoromethylation of (hetero)aromatics required the use of potassium persulfate as an additive and the mono- or bis-trifluoromethylated adducts were obtained, depending on the actual reaction conditions and the chosen substrate.
- Corsico, Sara,Fagnoni, Maurizio,Ravelli, Davide
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p. 1375 - 1380
(2017/09/23)
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- Phosphovanadomolybdic acid catalyzed direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 as the CF3 source and O2 as the terminal oxidant
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A direct C-H trifluoromethylation of (hetero)arenes using NaSO2CF3 (Langlois' reagent) as the CF3 source and O2 as the terminal oxidant has been developed. In the presence of catalytic amounts of phosphovanadomolybdic acids, such as H6PV3Mo9O40, various kinds of substituted benzenes and heteroaromatic compounds could be converted into the corresponding trifluoromethylated products.
- Li, Chifeng,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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supporting information
p. 1417 - 1420
(2017/02/23)
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- Metal-Free, Initiator-Free Graphene Oxide-Catalyzed Trifluoromethylation of Arenes
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The direct C?H trifluoromethylation of arenes catalyzed by graphene oxide (GO) under safe conditions is described. This strategy is metal-free, initiator-free, safe, and scalable. It employs a readily available CF3 source and the reaction can b
- Zhang, Jingyu,Yang, Yun,Fang, Jingxian,Deng, Guo-Jun,Gong, Hang
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p. 2524 - 2527
(2017/09/11)
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- METHOD FOR PREPARATION OF FLUORO, CHLORO AND FLUOROCHLORO ALKYLATED COMPOUNDS BY HOMOGENEOUS CATALYSIS
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The invention discloses a method for preparation of fluoro, chloro and fluorochloro alkylated compounds by homogeneous Pd catalyzed fluoro, chloro and fluorochloro alkylation with fluoro, chloro and fluorochloroalkyl halides in the presence of di(1-adamantyl)-n-butylphosphine and in the presence of 2,2,6,6-tetramethylpiperidine 1-oxyl.
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Page/Page column 15; 16; 21
(2016/06/01)
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- Palladium-Catalyzed Trifluoromethylation of (Hetero)Arenes with CF3Br
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The CF3 group is an omnipresent motif found in many pharmaceuticals, agrochemicals, catalysts, materials, and industrial chemicals. Despite well-established trifluoromethylation methodologies, the straightforward and selective introduction of such groups into (hetero)arenes using available and less expensive sources is still a major challenge. In this regard, the selective synthesis of various trifluoromethyl-substituted (hetero)arenes by palladium-catalyzed C-H functionalization is herein reported. This novel methodology proceeds under comparably mild reaction conditions with good regio- and chemoselectivity. As examples, trifluoromethylations of biologically important molecules, such as melatonin, theophylline, caffeine, and pentoxifylline, are showcased.
- Natte, Kishore,Jagadeesh, Rajenahally V.,He, Lin,Rabeah, Jabor,Chen, Jianbin,Taeschler, Christoph,Ellinger, Stefan,Zaragoza, Florencio,Neumann, Helfried,Brückner, Angelika,Beller, Matthias
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supporting information
p. 2782 - 2786
(2016/02/27)
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- Simple and Clean Photoinduced Aromatic Trifluoromethylation Reaction
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We describe a simple, metal-and oxidant-free photochemical strategy for the direct trifluoromethylation of unactivated arenes and heteroarenes under either ultraviolet or visible light irradiation. We demonstrated that photoexcited aliphatic ketones, such as acetone and diacetyl, can be used as promising low-cost radical initiators to generate CF3 radicals from sodium triflinate efficiently. The broad utility of this strategy and its benefit to medicinal chemistry are demonstrated by the direct trifluoromethylation of unprotected bidentate chelating ligand, xanthine alkaloids, nucleosides, and related antiviral drug molecules.
- Li, Lu,Mu, Xiaoyue,Liu, Wenbo,Wang, Yichen,Mi, Zetian,Li, Chao-Jun
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p. 5809 - 5812
(2016/06/09)
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- Metal-free radical perfluoroalkylation of (hetero)arenes
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We report a metal-free radical perfluoroalkylation method which uses inexpensive and commercially available perfluorocarboxylic anhydrides as an easy to use source of perfluoroalkyl radicals. This approach allows the perfluoroalkylation of different arenes, such as benzene derivatives, furans, thiophenes, and pyrroles, including highly functionalized compounds.
- Zhong, Sabilla,Hafner, Andreas,Hussal, Christoph,Nieger, Martin,Br?se, Stefan
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p. 6255 - 6258
(2015/02/19)
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- Metal-free direct C-H perfluoroalkylation of arenes and heteroarenes using a photoredox organocatalyst
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We report the visible-light-induced trifluoromethylation of arenes and heteroarenes using sodium trifluoromethanesulfinate catalyzed by anthraquinone-2-carboxylic acid. This reaction is a metal-free trifluoromethylation of arenes and heteroarenes catalyzed by a photoredox organocatalyst. Perfluoroalkylated arenes were also produced using sodium perfluoroalkylsulfinates.
- Cui, Lei,Matusaki, Yoko,Tada, Norihiro,Miura, Tsuyoshi,Uno, Bunji,Itoh, Akichika
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supporting information
p. 2203 - 2207
(2013/10/01)
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- Transition-metal-free oxidative trifluoromethylation of unsymmetrical biaryls with trifluoromethanesulfinate
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A transition-metal-free direct oxidative trifluoromethylation of unsymmetrical biaryls has been achieved by the simple combination of trifluoromethanesulfinate and phenyliodine bis(trifluoroacetate). The trifluoromethylation is selectively observed in the electron-rich arenes.
- Yang, Yu-Dong,Iwamoto, Kanji,Tokunaga, Etsuko,Shibata, Norio
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supporting information
p. 5510 - 5512
(2013/06/27)
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- Silver-catalysed trifluoromethylation of arenes at room temperature
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A variety of heteroarenes and electron rich arenes can be trifluoromethylated at room temperature with TMSCF3, catalytic silver and PhI(OAc)2.
- Seo, Sangwon,Taylor, John B.,Greaney, Michael F.
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supporting information
p. 6385 - 6387
(2013/08/23)
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- Silver-mediated trifluoromethylation of arenes using TMSCF3
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The silver-mediated C-H trifluoromethylation of aromatic substrates using TMSCF3 is described. The development, optimization, and scope of these transformations are reported. AgCF3 intermediates are proposed.
- Ye, Yingda,Lee, Shin Hee,Sanford, Melanie S.
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supporting information; experimental part
p. 5464 - 5467
(2011/12/05)
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- Copper-catalyzed trifluoromethylation of aryl boronic acids using a CF 3+ reagent
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A copper-catalyzed process for trifluoromethylation of aryl, heteroaryl, and vinyl boronic acids has been developed. The reaction is conducted under mild conditions and shows tolerance to moisture and a variety of functional groups.
- Xu, Jun,Luo, Dong-Fen,Xiao, Bin,Liu, Zhao-Jing,Gong, Tian-Jun,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 4300 - 4302
(2011/06/21)
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- Trifluoromethylation Reactions with Potassium Trifluoromeyhnesulfinate under Electrochemical Oxidation
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The electrochemical oxidation of potassium trifluoromethanesulfinate (CF3SO2K) in the presence of electron-rich aromatics and alkenes provides the corresponding trifluoromethylated products.
- Tommasino, Jean-Bernard,Brondex, Anne,Medebielle, Maurice,Thomalla, Marc,Langlois, Bernard R.
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p. 1696 - 1699
(2007/10/03)
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- Reactions of Perfluoroalkanesulfonyl Chlorides with Aromatic Compounds Catalyzed by a Ruthenium(II) Complex
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The reactions of perfluoroalkanesulfonyl chlorides with aromatic compounds in the presence of a catalytic amount of dichlorotris(triphenylphosphine)ruthenium(II) were found to give perfluoroalkylated compounds in good yield.
- Kamigata, Nobumasa,Fukushima, Takamasa,Yoshida, Masato
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p. 649 - 650
(2007/10/02)
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- Synthesis and Reactivity of N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide as a New Type of Trifluoromethylating Agent
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N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide (TNS-Tf) was synthesized in a 58 percent yield by the reaction of trifluoronitrosomethane with hydroxylamine followed by the treatment with trifluoromethanesulfonyl fluoride in the presence of a base.TNS-Tf was demonstrated to be an effective trifluoromethylating agent photochemically or thermally for aromatics, thiols, disulfides, and uridine derivatives.The insertion reaction by two trifluoromethyl groups of TNS-Tf to the sulfur-sulfur bonds was observed in the reaction with disulfides having electron-withdrawing groups, giving 2 mols of trifluoromethylthio compounds.Furthermore, TNS-Tf served as a good reagent for mild and convenient in situ generation of trifluoromethylcopper complex which converted iodoaromatics to trifluoromethyl-substituted aromatics in good yields.Similarly, N-trifluoromethyl-N-nitrosononafluoro-1-butanesulfonamide (TNS-Nf) was synthesized in a 36 percent yield.The examination of the reactivity indicated that this type of N-nitroso sulfonamides became to be sources of both perfluoroalkyl radicals contained.
- Umemoto, Teruo,Ando, Akira
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p. 447 - 452
(2007/10/02)
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- N-TRIFLUOROMETHYL-N-NITROSOBENZENESULFONAMIDE. A NEW TRIFLUOROMETHYLATING AGENT.
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N-Trifluoromethyl-N-nitrosobenzenesulfonamide was synthesited.It was demonstrated that it acted as a new trifluoromethylating agent.
- Umemoto, Teruo,Miyano, Osamu
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p. 3929 - 3930
(2007/10/02)
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