- Electrochemical initiation by sulfur dioxide of radical-chain trifluoromethylation processes of thiophenols with bromotrifluoromethane
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Sulfur dioxide may serve as an efficient catalyst for the electrochemical trifluoromethylation of thiophenols by Freon F13B1 (CF3Br), which enables implementation of trifluoromethylation in an energy-saving radical-chain regime. - Keywords: Electrochemical trifluoromethylation; Thiophenols; Radical-chain processes; Bromotrifluoromethane; Sulfur dioxide catalyst
- Koshechko, V. G.,Kiprianova, L. A.,Fileleeva, L. I.,Rozhkova, Z. Z.
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Read Online
- Design and preparation of polyphenyl distance markers for solid-state 19F NMR
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With 13C-labeled samples, it is possible to measure internuclear distances up to 7 A by solid-state NMR, thus providing a powerful tool for probing ligand-receptor interactions. However, limitations in measurable distances and appreciable natur
- Monde, Kenji,Tomita, York,Gilchrist Jr., M. Lane,McDermott, Ann E.,Nakanishi, Koji
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Read Online
- Radical Aromatic Trifluoromethylthiolation: Photoredox Catalysis vs. Base Mediation
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Trifluoromethyl aryl sulfides (Ar-SCF3) constitute highly attractive building blocks due to their exceptional lipophilicity and chemical properties. Related protocols of radical aromatic trifluoro-methylthiolation of arenediazonium salts were developed that are based on the facile generation of intermediate aryl radicals. Their reactions with commercial F3CS-SCF3 under very mild conditions afforded a diverse set of Ar-SCF3 (3]Cl2} with the weak base-mediated dark reaction documented higher synthetic efficiency of the former but higher operational simplicity of the latter strategy.
- Koziakov, Denis,Majek, Michal,Jacobi von Wangelin, Axel
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Read Online
- Iridium(I)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate to access fluoroalkylthioethers
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A new method for the preparation of fluoroalkylthioethers including trifluoromethylthioether and difluoromethylthioether by iridium(I)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate was developed. In the reaction system, dimethyl diazomalonate was used as reducing reagent and the corresponding fluoroalkylthioethers were produced through oxygen atom transfer from fluoroalkylsulfoxides to diazomalonate. The protocol featuring effective oxygen atom transfer, mild reaction conditions and good functional groups tolerance offers an alternative strategy for the synthesis of fluoroalkylthioethers.
- Chen, Wenbo,Li, Wenlin,Lu, Wenqing,Xie, Yongbin,Zhou, Yicheng
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supporting information
(2022/03/16)
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- Gold (I/III)-Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides
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The first C?SCF3/SeCF3 cross-coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF3 or Me4NSeCF3, and organohalides as substrates are reported. The new methodology enables a one-stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio- and selenoethers with a broad substrate scope (>60 examples with up to 97 % isolated yield). The method is scalable, and its robustness is evidenced by the late-stage functionalization of various bioactive molecules, which makes this reaction an attractive alternative in the synthesis of trifluoromethylthio- and selenoethers for pharmaceutical and agrochemical research and development.
- Mudshinge, Sagar R.,Yang, Yuhao,Xu, Bo,Hammond, Gerald B.,Lu, Zhichao
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supporting information
(2022/02/10)
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- Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF3
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Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.
- Zheng, Changge,Jiang, Chao,Huang, Shuai,Zhao, Kui,Fu, Yingying,Ma, Mingyu,Hong, Jianquan
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supporting information
p. 6982 - 6986
(2021/09/08)
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- Metal-Free Trifluoromethylthiolation of Arylazo Sulfones
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A visible-light-driven protocol for the synthesis of aryl trifluoromethyl thioethers under photocatalyst- and metal-free conditions has been pursued. The procedure exploits the peculiar properties of arylazo sulfones (having electron-rich or electron-poor substituents on the (hetero)aromatic ring) as photochemical precursors of aryl radicals and S-trifluoromethyl arylsulfonothioates as easy-to-handle trifluoromethylthiolating agents.
- Li, Ankun,Li, Yuxuan,Liu, Junjie,Chen, Jingqi,Lu, Kui,Qiu, Di,Fagnoni, Maurizio,Protti, Stefano,Zhao, Xia
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p. 1292 - 1299
(2021/01/14)
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- Electrochemical Trifluoromethylation of Thiophenols with Sodium Trifluoromethanesulfinate
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We developed an electrochemical trifluoromethylation of thiophenols without the use of metal catalysts and oxidants. This reaction features mild reaction conditions, readily available substrate, as well as moderate to good yields. In addition, this protocol can be easily scaled up with moderate efficiency.
- Zhu, Xing-Xing,Wang, Huai-Qin,Li, Chen-Guang,Xu, Xiao-Lan,Xu, Jun,Dai, Jian-Jun,Xu, Hua-Jian
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p. 16114 - 16120
(2021/02/03)
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- Perfluoroalkylation of Thiosulfonates: Synthesis of Perfluoroalkyl Sulfides
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A practical synthesis of perfluoroalkyl sulfides is described. The method employs stable and readily accessible thiosulfonates as new electrophiles with commercial nucleophilic perfluoroalkylating reagents. The mild reaction conditions allow access to a wide variety of both aryl- and alkyl-substituted perfluoroalkyl sulfides amenable to pharmaceutical development. Furthermore, the reaction operation is straightforward, odorless, does not produce toxic wastes, and, therefore should appeal to practitioners in industrial-scale productions.
- Luo, Ziwei,Yang, Xinkan,Tsui, Gavin Chit
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supporting information
p. 6155 - 6159
(2020/07/30)
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- Copper(I)-promoted trifluoromethylthiolation of arenediazonium salts with AgSCF3
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An efficient method for trifluoromethylthiolation of arenediazonium salts has been developed in mild conditions with a stable and convenient AgSCF3. It provides a straightforward and convenient way for the synthesis of trifluoromethylthiolated compound from diazonium salts in moderate to good yields.
- Zheng, Changge,Liu, Yang,Hong, Jianquan,Huang, Shuai,Zhang, Wei,Yang, Yupeng,Fang, Ge
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supporting information
p. 1404 - 1407
(2019/05/01)
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- Transition-Metal-Free ipso-Trifluoromethylthiolation of Lithium Aryl Boronates
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A transition-metal-free direct trifluoromethylthiolation of the ipso-carbon of lithium aryl boronates with trifluoromethanesulfenate under mild conditions was described. In addition, late-stage site-selective C-H borylation/trifluoromethylation and C-Cl b
- Shen, Feng,Zheng, Hanliang,Xue, Xiao-Song,Lu, Long,Shen, Qilong
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p. 6347 - 6351
(2019/08/20)
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- A process for converting substituted phenyl diazonium salts into [(trifluoromethyl)thio]benzene
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The invention discloses a synthetic method of [(trifluoromethyl)thio]benzene compounds, particularly a method for converting substituted phenyl diazonium salts into [(trifluoromethyl)thio]benzene. Themethod comprises the following steps: under white light
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Paragraph 0086-0093
(2019/12/02)
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- Tf2O-Promoted Trifluoromethythiolation of Various Arenes Using NaSO2CF3
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A sulfonic anhydride-promoted direct trifluoromethylthiolation using NaSO2CF3 has been developed. The simple and practical strategy enabled the direct introduction of SCF3 moiety into unexplored arene scaffolds under reductant- and metal-free condition at room temperature. (Figure presented.).
- Liu, Jie,Zhao, Xiaochun,Jiang, Lvqi,Yi, Wenbin
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supporting information
p. 4012 - 4016
(2018/09/20)
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- A novel method for preparing S-(perfluoroalkyl)-dibenzothiophenium trifluoromethanesulfonate
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A method for preparing S-(perfluoroalkyl)-dibenzothiophenium trifluoromethanesulfonate shown as a general formula (I) by a one-pot process with significant effects is disclosed by the invention. The method includes reacting a biphenyl compound, perfluoroalkyl sulfonate, trifluoroacetic anhydride and trifluoromethanesulfonic acid. The biphenyl compound can be recovered and utilized so that the method is an environmentally friendly preparing method.
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Paragraph 0100; 0104
(2018/04/01)
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- Metal-free trifluoromethylthiolation of arenediazonium salts with Me4NSCF3
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A metal-free entry to the pharmaceutically meaningful substrate class of trifluoromethyl thioethers has been developed starting from widely available arenediazonium salts and commercially available Me4N+SCF3?. This reaction proceeds within one hour at 0 °C and is applicable to a wide range of functionalized substrates.
- Bertoli, Giulia,Exner, Benjamin,Evers, Mathies V.,Tschulik, Kristina,Goo?en, Lukas J.
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p. 132 - 136
(2018/04/05)
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- Fluorodecarboxylation: Synthesis of aryl trifluoromethyl ethers (ArOCF3) and thioethers (ArSCF3)
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Fluorodecarboxylation of aryloxydifluoroacetic acid (ArOCF2CO2H) and arylmercaptodifluoroacetic acid (ArSCF2CO2H) towards ArXCF3 (X = O, S) using silver (I) salts in the presence of Selectfluor in a biphasic system with trifluoroacetic acid additive is discussed.
- Krishanmoorthy, Sankarganesh,Schnell, Simon D.,Dang, Huong,Fu, Fang,Prakash, G.K. Surya
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p. 130 - 135
(2017/09/06)
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- Cu-mediated oxidative trifluoromethylthiolation of arylboronic acids with (bpy)CuSCF3
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An efficient trifluoromethylthiolation reaction of arylboronic acids with (bpy)CuSCF3in the presence of oxygen at room temperature is described. This method produces a variety of aryl trifluoromethylthioether derivatives in good to high yield. The mechanism of this trifluoromethylthiolation is discussed as well.
- Zhao, Mingzhu,Zhao, Xiaoming,Zheng, Purui,Tian, Yawei
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- Silver-catalyzed fluoroalkylation of thiols using fluoroalkanesulfinates
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A practical sliver-catalyzed fluoroalkylation of aryl-, heteroaryl- and alkylthiols has been developed. The reaction has a good functional-group tolerance and excellent selectivity. A variety of stable and solid fluoroalkanesulfinates including di- and perfluoroalkanesulfinates can be employed. This methodology provides a straightforward and streamlined access to perfluoroalkylthiolated organic molecules. [Figure presented]
- Ma, Jing-jing,Liu, Qi-ran,Lu, Guo-ping,Yi, Wen-bin
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supporting information
p. 113 - 117
(2017/01/03)
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- O-Trifluoromethylation of Phenols: Access to Aryl Trifluoromethyl Ethers by O-Carboxydifluoromethylation and Decarboxylative Fluorination
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A new strategy for the synthesis of aryl trifluoromethyl ethers (ArOCF3) by combining O-carboxydifluoromethylation of phenols and subsequent decarboxylative fluorination is reported. This protocol allows easy construction of functionalized trifluoromethoxybenzenes and trifluoromethylthiolated arenes (ArSCF3) in moderate to good yields. Moreover, it utilizes accessible and inexpensive reagents sodium bromodifluoroacetate and SelectFluor II and, thus, is practical for O-trifluoromethylation of phenols. The potential application of this method is demonstrated with the preparation of a plant-growth regulator, Flurprimidol.
- Zhou, Min,Ni, Chuanfa,He, Zhengbiao,Hu, Jinbo
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supporting information
p. 3754 - 3757
(2016/08/16)
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- Trifluoromethylthiolation of Unsymmetrical λ3-Iodane Derivatives: Additive-Free, Selective and Scalable Introduction of the SCF3 Group
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The reaction of copper trifluoromethyl sulfide with diaryliodonium salts provides a straightforward pathway for the synthesis of aryl trifluoromethyl thioethers under mild reaction conditions and within short reaction times. High chemoselectivity was achieved by using mesityl as a leaving group. A large range of novel [(het)aryl](mesityl)iodonium salts underwent this reaction under the optimized conditions to give the desired products in moderate to good yields.
- Nikolaienko, Pavlo,Yildiz, Tülay,Rueping, Magnus
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p. 1091 - 1094
(2016/03/05)
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- Sandmeyer-Type Trifluoromethylthiolation and Trifluoromethylselenolation of (Hetero)Aromatic Amines Catalyzed by Copper
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Aromatic and heteroaromatic diazonium salts were efficiently converted into the corresponding trifluoromethylthio- or selenoethers by reaction with Me4NSCF3 or Me4NSeCF3, respectively, in the presence of catalytic amounts of copper thiocyanate. These Sandmeyer-type reactions proceed within one hour at room temperature, are applicable to a wide range of functionalized molecules, and can optionally be combined with the diazotizations into one-pot protocols.
- Matheis, Christian,Wagner, Victoria,Goossen, Lukas J.
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supporting information
p. 79 - 82
(2016/01/25)
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- Trifluoromethylation of thiophenols and thiols with sodium trifluoromethanesulfinate and iodine pentoxide
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A selective and facile trifluoromethylation process for a wide range of thiophenols and thiols under metal free conditions has been developed using two simple and safe solids, sodium trifluoro-methanesulfinate and iodine pentoxide, via the radical process.
- Ma, Jing-Jing,Yi, Wen-Bin,Lu, Guo-Ping,Cai, Chun
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p. 417 - 421
(2016/02/03)
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- Iron-Catalyzed Decarboxylation of Trifluoroacetate and Its Application to the Synthesis of Trifluoromethyl Thioethers
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Nucleophilic CF3 has been generated by decarboxylation of potassium trifluoroacetate, arguably the most easy-to-handle, inexpensive, and sustainable source of trifluoromethyl groups. Simple iron(II) chloride catalyzes the decarboxylation as well as a subsequent trifluoromethylation of organothiocyanates, resulting in a straightforward synthesis of trifluoromethyl thioethers. The KCN byproduct is absorbed by iron(II) with formation of nontoxic potassium hexacyanoferrate. An analogous trifluoromethylation of aldehydes with trifluoroacetate underlines the synthetic potential of such iron-catalyzed decarboxylative trifluoromethylations.
- Exner, Benjamin,Bayarmagnai, Bilguun,Jia, Fan,Goossen, Lukas J.
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p. 17220 - 17223
(2016/01/25)
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- Copper-Catalyzed Trifluoromethylthiolation of Di(hetero)aryl-λ3-iodanes: Mechanistic Insight and Application to Synthesis of (Hetero)Aryl Trifluoromethyl Sulfides
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The direct and regioselective copper/S-Phos-catalyzed trifluoromethylthiolation of symmetrical and unsymmetrical di(hetero)aryl-λ3-iodanes has been accomplished for the synthesis of various (hetero)aryl trifluoromethyl sulfides employing readily accessible silver trifluoromethylthiolate (AgSCF3) as nucleophilic trifluoromethylthiolating reagent. The developed transformation tolerates various functional groups like nitrile, enolizable ketone, ester, nitro and free carboxylic acid. Interestingly, the formal trifluoromethylthiolation of arenes was also achieved through integration of the synthesis of diaryl-λ3-iodanes from arenes with the trifluoromethylthiolation. Mechanistic investigations did not favor the radical formation and SET pathway. Based on the variable temperature 19F NMR spectroscopy, isolation of the most relevant catalytic intermediate, and stoichiometric studies supported the Cu(I)/Cu(III) catalytic cycle, wherein the oxidative addition of diaryl-λ3-iodanes was assisted by the silver salt.
- Saravanan, Perumal,Anbarasan, Pazhamalai
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supporting information
p. 3521 - 3528
(2016/01/25)
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- Mild and Soft Catalyzed Trifluoromethylthiolation of Boronic Acids: The Crucial Role of Water
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The most reactive 2nd generation of trifluoromethanesulfenamides undergoes a copper-catalyzed cross-coupling reaction with boronic acids to afford CF3S-molecules. Contrary to the previous methods in the literature, no base addition, no heating, and no large excess of reagents are required to obtain good results. Furthermore, a crucial role of a small amount of water to favor this reaction has been demonstrated. This constitutes the mildest described conditions for such a reaction.
- Glenadel, Quentin,Alazet, Sébastien,Tlili, Anis,Billard, Thierry
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supporting information
p. 14694 - 14698
(2015/10/19)
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- A mild and fast photocatalytic trifluoromethylation of thiols in batch and continuous-flow
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S-CF3 bonds are important structural motifs in various pharmaceutical and agrochemical compounds. However, their preparation remains a major challenge in synthetic organic chemistry. Here, we report the development of a mild and fast photocatalytic trifluoromethylation of thiols. The combination of commercially available Ru(bpy)3Cl2, visible light and inexpensive CF3I gas proved to be an efficient method for the direct trifluoromethylation of thiols. The protocol is demonstrated on a wide range of aromatic, hetero-aromatic and aliphatic substrates in both batch and continuous microflow (32 examples, 52-98% yield). Process intensification through continuous microflow application resulted in a 15-fold increase in production rate (0.25 mmol min-1) due to improved gas-liquid mass transfer, enhanced irradiation as well as convenient handling of the gaseous CF3 source. Furthermore, the efficiency of the flow process allowed to reduce the amount of CF3I (1.1 equivalent) to reach full conversion. This journal is
- Straathof, Natan J. W.,Tegelbeckers, Bart J. P.,Hessel, Volker,Wang, Xiao,Nol, Timothy
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p. 4768 - 4773
(2015/01/09)
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- An electrophilic hypervalent iodine reagent for trifluoromethylthiolation
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Sulfur and friends: A new electrophilic hypervalent iodine reagent 1 has been developed for direct trifluoromethylthiolation. A variety of nucleophiles, including β-ketoesters, aldehydes, amides, aryl or vinyl boronic acids, and alkynes, reacted with 1 under mild conditions to give the corresponding trifluoromethylthiolated compounds in good to excellent yields.
- Shao, Xinxin,Wang, Xueqiang,Yang, Tao,Lu, Long,Shen, Qilong
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supporting information
p. 3457 - 3460
(2013/04/24)
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- Copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with CF3CO2Na and elemental sulfur
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A practical three-component copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with cheap and readily available sodium trifluoroacetate and elemental sulfur is reported. A variety of trifluoromethylthio-substituted aromatics are synthesized in moderate yields under mild reaction conditions.
- Zhai, Lijuan,Li, Yaming,Yin, Jun,Jin, Kun,Zhang, Rong,Fu, Xinmei,Duan, Chunying
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p. 10262 - 10266
(2013/11/19)
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- Copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with TMSCF3 and elemental sulfur
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Fluorinated functionality: The copper-catalyzed oxidative trifluoromethylthiolation of aryl boronic acids with TMSCF3 and elemental sulfur at room temperature is described for the first time. This reaction provides a concise and efficient method for the synthesis of aryl trifluoromethyl thioethers (ArSCF3) under mild conditions. Phen=Phenanthroline. Copyright
- Chen, Chao,Xie, Yan,Chu, Lingling,Wang, Ruo-Wen,Zhang, Xingang,Qing, Feng-Ling
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supporting information; experimental part
p. 2492 - 2495
(2012/05/20)
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- Convenient synthesis and isolation of trifluoromethylthio-substituted building blocks
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Various aryl-, heteroaryl-, and alkyl mercaptanes (RSH, 1a-r) were treated with a slight excess of NaH suspended in DMF to make the appropriate sodium thiolates (RSNa), which then reacted with 1.3 equivalent of CF3I at room temperature for overnight to afford the appropriate trifluoromethyl sulfides (CF3SR, 2) in fair to good yields. The radical chain alkylation reaction was effective without the use of UV irradiation with all but three substrates (thiosalicylic acid, 1k; 2-mercaptobenzimidazole, 1q; and 3-mercaptopropionic acid, 1r). Steam-distillation was found as an effective and easy to upscale means for the isolation of these volatile and water immiscible sulfides. The CF3I reagent gas was conveniently weighed and delivered to the reaction mixture by the balloon technique or as a preliminary made stock solution in DMF or DMSO. The sulfides 2 obtained here were assayed by GC and characterized by 1H, 13C, 19F NMR and MS spectroscopy.
- Harsányi, Antal,Dorkó, éva,Csapó, ágnes,Bakó, Tibor,Peltz, Csaba,Rábai, József
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experimental part
p. 1241 - 1246
(2011/11/12)
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- Synthesis of aryl perfluoroalkyl sulfides from aromatic disulfides
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Thermolysis of xenon(II) bis(perfluoroalkanecarboxylates) in the presence of diaryl disulfides occurs through the S-S bond cleavage to form dihalo-, halonitro-, and halodinitrophenyl perfluoroalkyl sulfides. The latter type of compounds was obtained for the first time. The main side process is the perfluoroalkylation of the aromatic ring.
- Sipyagin,Enshov,Kashtanov,Potemkin,Thrasher,Waterfeld
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p. 420 - 434
(2007/10/03)
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- Nonlinear Optical Epoxy Polymers with Polar Tolan Chromophores
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A variety of optically nonlinear tolan chromophores and epoxy based polymers containing them have been prepared and studied.The molecular hyperpolarizabilities of the dye chromophores have been measured by the EFISH technique while the polymers containing
- Twieg, R.,Ebert, M.,Jungbauer, D.,Lux, M.,Reck, B.,et al.
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