- One-Pot Successive Turbo Grignard Reactions for the Facile Synthesis of α-Aryl-α-Trifluoromethyl Alcohols
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A novel straightforward one-pot methodology for two successive turbo Grignard reagent (iPrMgCl·LiCl) reactions, was developed for a facile synthesis of α-aryl-α-trifluoromethyl alcohols, motifs of value in pharmaceutical chemistry. The method displayed broad functional group tolerance, including reducible groups. Dual roles of iPrMgCl·LiCl were exploited in the tandem reaction with commercially available iodoarenes or iodoheteroarenes and 2,2,2-trifluoroethyl trifluoroacetate. The process encompasses three successive reactions in a one-pot process: the iPrMgCl·LiCl-mediated iodine/magnesium-exchange reaction of iodoarenes or iodoheteroarenes; nucleophilic addition of various generated aryl or heteroarylmagnesium reagents to 2,2,2-trifluoroethyl trifluoroacetate; and the reduction of in-situ generated aryl trifluoromethyl ketones with iPrMgCl·LiCl, to produce the corresponding α-aryl or α-heteroaryl-α-trifluoromethyl alcohols bearing various substituents, including reducible functional groups in good to excellent yields.
- Kani, Ryunosuke,Inuzuka, Toshiyasu,Kubota, Yasuhiro,Funabiki, Kazumasa
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supporting information
p. 4487 - 4493
(2020/06/01)
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- Synthesis of Unsymmetric Triarylmethanes Bearing CF 3-Substituted All-Carbon Quaternary Stereocenters: 1,6-Arylation of δ-Trifluo romethyl Substituted para -Quinone Methides
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Pre-synthesized δ-CF 3-δ-aryl-disubstituted para -quinone methides bearing δ-substituents were identified as isolable and storable substrates for 1,6-arylation reactions. A broad range of electron-rich arenes and heteroarenes participated in the arylation process, furnishing a wide array of unsymmetrical CF 3-substituted triarylmethanes in high efficiency. The mild and expeditious protocol exhibited broad scopes of both arene and para -quinone methide components.
- Ma, Yingang,Pang, Jingxiang,Pan, Xiaoguang,Ma, Shutao,Liu, Xigong,Liu, Lei
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supporting information
p. 1619 - 1622
(2020/09/15)
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- Gas/Liquid-Phase Micro-Flow Trifluoromethylation using Fluoroform: Trifluoromethylation of Aldehydes, Ketones, Chalcones, and N-Sulfinylimines
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A micro-flow nucleophilic trifluoromethylation of carbonyl compounds using gaseous fluoroform was developed. This method also allows the first micro-flow transformation of N-sulfinylimines into trifluoromethyl amines with excellent diastereoselectivity. To demonstrate the synthetic utility of this micro-flow synthesis, the formal micro-flow synthesis of Efavirenz is described.
- Hirano, Kazuki,Gondo, Satoshi,Punna, Nagender,Tokunaga, Etsuko,Shibata, Norio
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p. 406 - 410
(2019/02/13)
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- Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling of Secondary α-(Trifluoromethyl)benzyl Tosylates
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A palladium-catalyzed C(sp3)?C(sp2) Suzuki–Miyaura cross-coupling of aryl boronic acids and α-(trifluoromethyl)benzyl tosylates is reported. A readily available, air-stable palladium catalyst was employed to access a wide range of functionalized 1,1-diaryl-2,2,2-trifluoroethanes. Enantioenriched α-(trifluoromethyl)benzyl tosylates were found to undergo cross-coupling to give the corresponding enantioenriched cross-coupled products with an overall inversion in configuration. The crucial role of the CF3 group in promoting this transformation is demonstrated by comparison with non-fluorinated derivatives.
- Brambilla, Marta,Tredwell, Matthew
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supporting information
p. 11981 - 11985
(2017/09/20)
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- Synthesis of Perfluoroalkyl-Substituted Vinylcyclopropanes by Way of Enhanced Neighboring Group Participation
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A simple, high yielding, two-step, one-pot protocol for the preparation of trifluoromethyl-substituted vinylcyclopropanes from α-CF3 homoallyl alcohols is disclosed. Destabilization of the cationic intermediate by the electron-withdrawing CF3 group greatly enhances neighboring group participation of the alkene, allowing ring closure to predominate. The reaction can be extended to the difluoromethyl and pentafluoroethyl group, enabling the preparation of a diverse array of fluoroalkyl-substituted vinylcyclopropanes. A diverse array of fluoroalkyl-substituted vinylcyclopropanes are prepared in a simple, high-yielding, two-step, one-pot protocol by means of cationic ring-closure.
- Kelly, Christopher B.,Mercadante, Michael A.,Carnaghan, Emma R.,Doherty, Matthew J.,Fager, Diana C.,Hauck, John J.,Macinnis, Allyson E.,Tilley, Leon J.,Leadbeater, Nicholas E.
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p. 4071 - 4076
(2015/06/30)
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- Catalytic highly enantioselective transfer hydrogenation of β-trifluoromethyl nitroalkenes. An easy and general entry to optically active β-trifluoromethyl amines
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In the presence of a thiourea catalyst, β-CF3 nitroalkenes react with Hantzsch esters in a highly enantioselective fashion, giving a broad range of β-CF3 amine precursors with a tertiary stereocentre at the β-position. This reaction
- Martinelli, Emilie,Vicini, Anna Chiara,Mancinelli, Michele,Mazzanti, Andrea,Zani, Paolo,Bernardi, Luca,Fochi, Mariafrancesca
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supporting information
p. 658 - 660
(2015/01/09)
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- Nucleophilic trifluoromethylation of carbonyl compounds: Trifluoroacetaldehyde hydrate as a trifluoromethyl source
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A feasible nucleophilic trifluoromethylating protocol has been developed using trifluoroacetaldehyde hydrate as an atom-economical trifluoromethyl source. The reaction was found to be applicable to the nucleophilic trifluoromethylation of a broad spectrum of carbonyl compounds with satisfactory yields in general. DFT calculations have been performed to provide mechanistic insight into the present and related reactions employing 2,2,2-trifluoro-1- methoxyethanol and hexafluoroacetone hydrate.
- Surya Prakash,Zhang, Zhe,Wang, Fang,Munoz, Socrates,Olah, George A.
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p. 3300 - 3305
(2013/06/27)
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- Nonenzymatic kinetic resolution of racemic 2,2,2-trifluoro-1-aryl ethanol via enantioselective acylation
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Kinetic resolution of a series of 2,2,2-trifluoro-1-aryl ethanol with (R)-benzotetramisole as the catalyst has been investigated. The result showed that when the aryl group in the substrate was a phenyl (or a phenyl substituted by an electron-donating group) or a naphthyl (an extended phenyl) group, the system could give an s value higher than 20. Preparative KR examples demonstrated the applicability of this method in the preparation of some of enantiomerically pure 2,2,2-trifluoro-1-aryl ethanol or 2,2,2-trifluoro-1-aryl-ethyl iso-butyrate.
- Xu, Qing,Zhou, Hui,Geng, Xiaohong,Chen, Peiran
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supporting information; experimental part
p. 2232 - 2238
(2009/07/11)
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- Reduction of 2,2,2-trifluoro-1-arylethanones with alkyl phosphines
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In the presence of alkyl phosphines, reduction of 2,2,2-trifluoro-1-arylethanones proceeded smoothly to give the corresponding reduction products in moderate to high yields at room temperature. The possible mechanism was discussed on the basis of deuteriu
- Shi, Min,Liu, Xu-Guang,Guo, Ying-Wen,Zhang, Wen
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p. 12731 - 12734
(2008/03/15)
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- Sodium trifluoroacetate: An efficient precursor for the trifluoromethylation of aldehydes
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In a convenient and efficient procedure, the nucleophilic trifluoromethylation of aldehydes with sodium trifluoroacetate was achieved, using copper(I) halides as the catalyst.
- Chang, Ying,Cai, Chun
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p. 3161 - 3164
(2007/10/03)
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- A chiral triaminosulfonium salt: Design and application to catalytic asymmetric synthesis
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The first chiral triaminosulfonium salt, tris((S,S)-3,4-diphenylpyrrolidino)sulfonium difluorotriphenylstannate, catalyzes trifluoromethylation of benzaldehyde with (trifluoromethyl)trimethylsilane to give the corresponding optically active alcohol with 52% ee.
- Kuroki, Yoshichika,Iseki, Katsuhiko
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p. 8231 - 8234
(2007/10/03)
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- Coupling of fluoroform with aldehydes using an electrogenerated base
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Trifluoromethylated alcohols are easily obtained in a one pot electroreaction in which cathodic reduction of iodobenzene generates a strong base which deprotonates fluoroform, inducing its coupling with aldehydes.
- Barhdadi, Rachid,Troupel, Michel,Perichon, Jacques
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p. 1251 - 1252
(2007/10/03)
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- Intramolecular Reactivity of Arylcarbenes: Derivatives of o-Tolylcarbene
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Various CH2X groups have been attached to the ortho position of phenylcarbene.If 2'- or 3'-C-H bonds are present, as in 23 (X = Me), 71 (X = CMe3), and 58 (X = SiMe3), C-H insertion leading to five- or six-membered rings predominates in the gas phase and competes with intermolecular reactions in solution.The formation of benzocyclobutenes via insertion into 1'-C-H bonds is a very minor reaction path of 23 and 71.In contrast, 58 produces substantial amounts of the benzocyclobutene 59 by way of C-Si insertion, particularly in the gas phase.Insertion into the Si-Me bonds of 58 also occurs while the C-F bonds of 37 (X = CF3) and 50 (X = F) are inert.In the gas phase, 37 and 50 give mainly benzocyclobutenes whereas intermolecular reactions prevail in solution.The effects of sensitization and of solvent polarity suggest that benzocyclobutenes arise from singlet arylcarbenes.The amount of carbene-carbene rearrangement decreases in the order 7 (X = H) > 37 (X = CF3) > 23 (X = Me); no rearrangement was observed with 50 (X = F), 58 (X = SiMe3), and 71 (X = CMe3).
- Kirmse, Wolfgang,Konrad, Wolfgang,Schnitzler, Dirk
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p. 3821 - 3829
(2007/10/02)
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- PALLADIUM AND NICKEL-CATALYZED PERFLUOROALKYLATION OF ALDEHYDES USING ZINC AND PERFLUOROALKYL HALIDES
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A room temperature method for the conversion of perfluoroalkyl iodides to α-perfluoroalkyl carbinols under Pd or Ni catalysis is reported.The use of trifluoromethyl bromide provides an economical procedure for trifluoromethyl substituted carbinols.
- O'Reilly, Neil J.,Maruta, Masamichi,Ishikawa, Nobuo
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p. 517 - 520
(2007/10/02)
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