- The electrophilic trifluoromethyl radical CF3 · Application of the dual-parameter equation to the correlation analysis of relative rates of the trifluoromethylbromo addition reactions to 14 p-Y-substituted phenylacetylenes
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A rigorous procedure was applied to the measurement of the relative rates, i.e., kr(Y)=kY/kH, of the trifluoromethylbromo addition reactions to 14 p-Y-substituted phenylacetylenes (1-Y, with Y=F, Cl, Br, Me, tBu
- Jiang, Xi-Kui,Ji, Guo-Zhen,Xie, John Rong-Yuan
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Read Online
- A Readily Available Trifluoromethylation Reagent and Its Difunctionalization of Alkenes
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Trifluoromethyl substitution is notably popular in pharmaceuticals and agrochemicals; however, trifluoromethylated compounds normally rely on the use of cost-prohibitive or gaseous trifluoromethylating reagents, which diminishes the general applicability of these methods. Herein an efficient trifluoromethylation reagent trifluoromethylsulfonyl-pyridinium salt (TFSP) was reported, which can be readily prepared from cheap and easily available bulk industrial feedstocks. TFSP can generate a trifluoromethyl radical under photocatalysis and realize the effective azido- or cyano-trifluoromethylation reactions of alkenes.
- Zhang, Min,Lin, Jin-Hong,Xiao, Ji-Chang
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supporting information
p. 6079 - 6083
(2021/08/16)
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- Rapid Syntheses of [11C]Arylvinyltrifluoromethanes through Treatment of (E)-Arylvinyl(phenyl)iodonium Tosylates with [11C]Trifluoromethylcopper(I)
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We report a method for labeling arylvinyltrifluoromethanes with carbon-11 (t1/2 = 20.4 min) as representatives of a new radiolabeled chemotype that has potential for developing radiotracers for biomedical imaging with positron emission tomography. Treatme
- Jana, Susovan,Telu, Sanjay,Yang, Bo Yeun,Haskali, Mohammad B.,Jakobsson, Jimmy E.,Pike, Victor W.
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supporting information
p. 4574 - 4578
(2020/06/05)
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- Deoxyfluorination of acyl fluorides to trifluoromethyl compounds by FLUOLEAD/Olah's reagent under solvent-free conditions
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A new protocol enabling the formation of trifluoromethyl compounds from acyl fluorides has been developed. The combination of FLUOLEAD and Olah's reagent in solvent-free conditions at 70 °C initiated the significant deoxyfluorination of the acyl fluorides and resulted in the corresponding trifluoromethyl products with high yields (up to 99%). This strategy showed a great tolerance for various acyl fluorides containing aryloyl, (heteroaryl)oyl, or aliphatic acyl moieties, providing good to excellent yields of the trifluoromethyl products. Synthetic drug-like molecules were also transformed into the corresponding trifluoromethyl compounds under the same reaction conditions. A reaction mechanism is proposed.
- Liang, Yumeng,Taya, Akihito,Zhao, Zhengyu,Saito, Norimichi,Shibata, Norio
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p. 3052 - 3058
(2021/01/15)
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- Merging hypervalent iodine and sulfoximine chemistry: A new electrophilic trifluoromethylation reagent
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Electrophilic trifluoromethylation is at the forefront of methodologies available for the installation of the CF3 moiety to organic molecules; research in this field is largely spurred by the availability of stable and accessible trifluoromethy
- Kalim, Jorna,Duhail, Thibaut,Le, Thanh-Nghi,Vanthuyne, Nicolas,Anselmi, Elsa,Togni, Antonio,Magnier, Emmanuel
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p. 10516 - 10523
(2019/12/02)
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- Electrochemical Synthesis Strategy for Cvinyl-CF3 Compounds through Decarboxylative Trifluoromethylation
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An efficient decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids using the Langlois reagent as a trifluoromethyl precursor has been achieved by an electro-oxidative strategy. Under catalyst-free and external oxidant-free electrolysis
- Hong, Huanliang,Li, Yibiao,Chen, Lu,Li, Bin,Zhu, Zhongzhi,Chen, Xiuwen,Chen, Ling,Huang, Yubing
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p. 5980 - 5986
(2019/05/10)
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- Iron(III) Porphyrin Catalyzed Olefination of Aldehydes with 2,2,2-Trifluorodiazoethane (CF3CHN2)
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An efficient method for the iron(III) porphyrin catalyzed olefination of various aldehydes with 2,2,2-trifluorodiazoethane under neutral conditions is described. This transformation was shown to have a broad substrate scope and provide the corresponding CF3-substituted alkenes in good yields. The number of equivalents of PPh3 that is used in this reaction is crucial to the success of the olefination process. This reaction is a useful supplement to the synthetic applications of CF3CHN2.
- Lu, Yang,Huang, Chuyu,Liu, Chao,Guo, Yong,Chen, Qing-Yun
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p. 2082 - 2090
(2018/05/31)
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- Method for synthesizing olefin compound by photo-induced one-pot process
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The invention discloses a method for synthesizing an olefin compound by a photo-induced one-pot process. The method comprises the following step of subjecting a halohydrocarbon and an aldehyde compound to a reaction under the condition of irradiation in an inert atmosphere by taking alkali metal carbonate as a base, taking an organic phosphine compound as an adjuvant and taking a photosensitizer as a catalyst, thereby obtaining the olefin compound. According to the method disclosed by the invention, the olefin compound is produced from the halohydrocarbon and the aldehyde compound in a high-yield manner under the condition of irradiation in the inert atmosphere under normal-temperature reaction conditions by taking acetonitrile, DMF (N,N-dimethylformamide) or DMA (N,N-dimethylacetamide) asa solvent, taking an organic phosphine reagent as a reaction adjuvant, taking the alkali metal carbonate as the base and taking the photosensitizer as the catalyst. Compared with the conventional olefin synthesis methods, the method disclosed by the invention has the obvious advantages that the reaction raw materials are readily available, the tolerance to a variety of functional groups on halohydrocarbons and aldehydes is high, the yield is high, the separation and purification of a product are simple and convenient, and the like.
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Paragraph 0089-0091
(2018/11/03)
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- Enantioselective Copper-Catalyzed Defluoroalkylation Using Arylboronate-Activated Alkyl Grignard Reagents
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A copper-catalyzed system has been introduced for the enantioselective defluoroalkylation of linear 1-(trifluoromethyl)alkenes through C-F activation to synthesize various gem-difluoroalkenes as carbonyl mimics. For the first time, arylboronate-activated alkyl Grignard reagents were uncovered in this cross-coupling reaction. Mechanistic studies confirmed that the tetraorganoborate complexes generated in situ were the key reactive species for this transformation.
- Wang, Minyan,Pu, Xinghui,Zhao, Yunfei,Wang, Panpan,Li, Zexian,Zhu, Chendan,Shi, Zhuangzhi
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supporting information
p. 9061 - 9065
(2018/08/03)
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- Palladium-catalyzed geometrically selective hydrogenation of (Z)-trifluoromethyl alkenyl triflate: An efficient approach to (Z) or (E)-3,3,3-trifluoropropenyl derivatives
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A Pd-catalyzed hydrogenation of (Z)-trifluoromethyl alkenyl triflate providing either (Z)- or (E)-3,3,3-trifluoropropenyl derivatives with excellent divergent geometric control in good yield is described. Catalyzed by Pd(OAc)2/PPh3, the reduction of (Z)-trifluoromethyl alkenyl triflates with HSiEt3 gave (E)-3,3,3-trifluoropropenyl derivatives, and while using HCOOH/Et3N as the reducing agent, the (Z)-isomers were obtained through an elimination/hydrogenation tandem pathway. Both transformations showed excellent geometrical selectivity.
- Zhao, Yilong,Zhou, Yuhan,Zhang, Chunxia,Wang, Huan,Zhao, Jinfeng,Jin, Kun,Liu, Jihong,Liu, Jianhui,Qu, Jingping
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p. 5693 - 5700
(2017/07/22)
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- Domino Hydroboration/Trifluoromethylation of Alkynes Using Fluoroform-Derived [CuCF3]
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A domino hydroboration/trifluoromethylation (formal hydrotrifluoromethylation) of alkynes using the fluoroform-derived [CuCF3] reagent is achieved. Synthetically useful (E)-alkenyl-CF3 building blocks and 1,1-bis(trifluoromethyl)-substituted alkenes can be prepared under ambient conditions in one pot/one step from alkynes. The ultimate source of CF3 is the inexpensive industrial waste fluoroform.
- He, Lisi,Yang, Xinkan,Tsui, Gavin Chit
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p. 6192 - 6201
(2017/06/23)
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- Metal-free radical trifluoromethylation of β-nitroalkenes through visible-light photoredox catalysis
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A catalytic method for functional group interconversion is immensely important in modern sciences. Here, we report an efficient catalytic conversion of nitroalkenes to highly stereoselective 1-trifluoromethylalkenes at room temperature. This unprecedented metal-free photocatalytic strategy is simple and operates under visible-light irradiation using the commercially available CF3 source.
- Midya, Siba P.,Rana, Jagannath,Abraham, Thomas,Aswin, Bhaskaran,Balaraman, Ekambaram
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p. 6760 - 6763
(2017/07/10)
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- Photocatalytic alkene reduction by a B12-TiO2 hybrid catalyst coupled with C-F bond cleavage for: Gem -difluoroolefin synthesis
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Photocatalytic syntheses of gem-difluoroolefins were performed using the B12-TiO2 hybrid catalyst during the CC bond reduction of α-trifluoromethyl styrenes with C-F bond cleavage at room temperature under nitrogen. The gem-difluoroolefins were used as synthetic precursors for fluorinated cyclopropanes.
- Tian, Hui,Shimakoshi, Hisashi,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio
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supporting information
p. 9478 - 9481
(2017/09/01)
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- Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in Batch and Flow
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Styrenes represent a challenging class of substrates for current radical trifluoromethylation and hydrotrifluoromethylation methods due to a myriad of potential side reactions. Herein, we describe the development of mild, selective and broadly applicable photocatalytic trifluoromethylation and hydrotrifluoromethylation protocols for these challenging substrates. The methods use fac-Ir(ppy)3, visible light and inexpensive CF3I and can be applied to a diverse set of vinylarene substrates. The use of continuous-flow photochemical reaction conditions allowed to reduce the reaction time and increase the reaction selectivity.
- Straathof, Natan J. W.,Cramer, Sten E.,Hessel, Volker,No?l, Timothy
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supporting information
p. 15549 - 15553
(2016/12/09)
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- Silver(I)-catalyzed denitrative trifluoromethylation of β-nitrostyrenes with CF3SO2Na
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A novel and convenient approach to the synthesis of substituted β-trifluoromethyl styrenes via a silver(I)-catalyzed denitrative trifluoromethylation with CF3SO2Na under relatively mild conditions has been developed. This protocol delivered excellent stereoselectivity and showed wide substrate tolerance.
- Huang, Ping,Li, Yaming,Fu, Xinmei,Zhang, Rong,Jin, Kun,Wang, Wenxin,Duan, Chunying
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supporting information
p. 4705 - 4708
(2016/10/03)
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- Copper-Catalyzed Diastereoselective Synthesis of Trifluoromethylated Tetrahydrofurans
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The copper-catalyzed intramolecular diastereoselective trifluoromethylcycloetherification of homoallylic alcohols with Togni's reagent as trifluoromethylating reagent was realized under mild conditions. Various trifluoromethylated tetrahydrofurans were synthesized in moderate to good yields. Moreover, a wide range of common functional groups was tolerated.
- Wang, Yanan,Jiang, Min,Liu, Jin-Tao
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supporting information
p. 1322 - 1327
(2016/04/26)
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- Decarboxylative and Denitrative Trifluoromethylation for the Synthesis of Cvinyl-CF3 Compounds with Togni (II) Reagent
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A highly efficient dimethylformamide (DMF)-promoted decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids with Togni (II) reagent under metal-free conditions has been developed. The reactions showed good yields, high stereoselectivities and excellent functional group tolerance. Mechanistic studies confirmed that free-radical processes were involved in this system since the CF3 radical had been clearly trapped by scavengers. This method has been extended to the denitrative trifluoromethylation of β-nitrostyrenes in the presence of an iron(III) catalyst.
- Ma, Jing-Jing,Yi, Wen-Bin,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 3447 - 3452
(2016/01/25)
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- Facile synthesis of 1-trifluoromethylalkenes via the decarboxylation of α-trifluoromethyl-β-lactones
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DCC-mediated cyclodehydration of α-trifluoromethyl-β-hydroxy acids provides α-trifluoromethylated β-lactone intermediates, without loss of stereoselectivity. These lactones undergo facile decarboxylation providing a simple route to obtain both alkyl and aryl trifluoromethylated alkenes in excellent yields and stereoselectivity.
- Veeraraghavan Ramachandran,Otoo, Barnabas
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p. 12388 - 12390
(2015/08/03)
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- Sunlight-driven trifluoromethylation of olefinic substrates by photoredox catalysis: A green organic process
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The principles and utility of photoredox catalysis in organic synthesis are described. After a brief description of the features of the two types of catalytic photoredox processes following the reductive quenching cycle (RQC) and the oxidative quenching cycle (OQC), the discussion is focused on organic transformations based on OQC, in particular the trifluoromethylation of olefinic substrates with electrophilic trifluoromethylating reagents furnishing solvolytic addition products and substitution products. It is concluded that catalytic photoredox systems are green from the point of view of harmfulness, safety, and energy source (visible light, including sunlight). Future prospects of photoredox catalysis will be also discussed.
- Akita, Munetaka,Koike, Takashi
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p. 742 - 751
(2015/07/15)
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- Palladium catalyzed vinyltrifluoromethylation of aryl halides through decarboxylative cross-coupling with 2-(trifluoromethyl)acrylic acid
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An efficient Pd-catalyzed stereoselective vinyltrifluoromethylation of aryl halides, through decarboxylative cross-coupling with 2-(trifluoromethyl)acrylic acid is described. The ready availability of the starting materials, the high level of functional group tolerance, and excellent E/Z selectivity make this protocol a safe and operationally convenient strategy for efficient synthesis of vinyltrifluoromethyl derivatives.
- Kathiravan, Subban,Nicholls, Ian A.
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supporting information
p. 1874 - 1877
(2015/04/27)
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- Copper/silver-mediated decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids with CF3SO2Na
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A copper/silver-catalyzed decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids with CF3SO2Na was performed under relatively mild conditions. The reaction shows high E/Z selectivity and wide substrate tolerance. Ag2CO3 plays an important role in promoting the decarboxylation process. Georg Thieme Verlag Stuttgart New York.
- Yin, Jun,Li, Yaming,Zhang, Rong,Jin, Kun,Duan, Chunying
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supporting information
p. 607 - 612
(2014/03/21)
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- Combining photoredox-catalyzed trifluoromethylation and oxidation with dmso: Facile synthesis of α-trifluoromethylated ketones from aromatic alkenes
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Trifluoromethylated ketones are useful building blocks for organic compounds with a trifluoromethyl group. A new and facile synthesis of ketones with a trifluoromethyl substituent in the α-position proceeds through a one-pot photoredox-catalyzed trifluoromethylation-oxidation sequence of aromatic alkenes. Dimethyl sulfoxide (DMSO) serves as a key and mild oxidant under these photocatalytic conditions. Furthermore, an iridium photocatalyst, fac[Ir(ppy)3] (ppy=2-phenylpyridine), turned out to be crucial for the present photoredox process. Valuable α-CF3-substituted ketones can be synthesized from aromatic alkenes by combining photoredox-catalyzed trifluoromethylation and oxidation with DMSO. The iridium photocatalyst fac-[Ir(ppy)3] (ppy=2-phenylpyridine) plays key roles in this keto-trifluoromethylation. SET=single electron transfer.
- Tomita, Ren,Yasu, Yusuke,Koike, Takashi,Akita, Munetaka
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supporting information
p. 7144 - 7148
(2014/07/21)
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- Copper-mediated trifluoromethylation of aryl-, heteroaryl-, and vinyltrifluoroborates with Langlois' reagent
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An effortless and realistic procedure for the copper-mediated trifluoromethylation of aryl-, heteroaryl- and vinyltrifluoroborates with CF3 radicals generated from NaSO2CF3 and tert-butyl hydroperoxide (TBHP) is presented. The developed method produces trifluoromethyl arenes and -alkenes in good to excellent yields and a wide range of electronically and structurally diverse substrates are tolerated.
- Dubbaka, Srinivas Reddy,Salla, Manohar,Bolisetti, Raghu,Nizalapur, Shashidhar
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p. 6496 - 6499
(2014/02/14)
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- Controlled trifluoromethylation reactions of alkynes through visible-light photoredox catalysis
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The control of a reaction that can form multiple products is a highly attractive and challenging concept in synthetic chemistry. A set of valuable CF3-containing molecules, namely trifluoromethylated alkenyl iodides, alkenes, and alkynes, were selectively generated from alkynes and CF 3I by environmentally benign and efficient visible-light photoredox catalysis. Subtle differences in the combination of catalyst, base, and solvent enabled the control of reactivity and selectivity for the reaction between an alkyne and CF3I. Variety through selectivity: Highly valuable trifluoromethylated alkenyl iodides, alkenes, and alkynes were selectively generated from alkynes and CF3I by environmentally benign and efficient visible-light photoredox catalysis. A suitable choice of catalyst, base, and solvent was crucial for the reactivity and selectivity of these processes.
- Iqbal, Naeem,Jung, Jaehun,Park, Sehyun,Cho, Eun Jin
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supporting information
p. 539 - 542
(2014/01/23)
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- Copper-catalyzed trifluoromethylation of aryl- and vinylboronic acids with generation of CF3-radicals
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The selective trifluoromethylation of aryl- and vinylboronic acids proceeds smoothly with CF3SO2Na (Langlois reagent) in the presence of copper catalysts and t-BuOOH. Therefore, the method relies both on transition metal catalysis an
- Li, Yang,Wu, Lipeng,Neumann, Helfried,Beller, Matthias
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supporting information
p. 2628 - 2630
(2013/04/23)
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- Visible-light-induced synthesis of a variety of trifluoromethylated alkenes from potassium vinyltrifluoroborates by photoredox catalysis
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A facile synthesis of trifluoromethylated alkenes by the radical-mediated trifluoromethylation of vinyltrifluoroborates has been developed. Togni's reagent serves as a CF3 radical precursor in the presence of the photoredox catalyst [Ru(bpy)3](PF6)2 under visible light irradiation. This new photocatalytic protocol can be applicable to a wide variety of vinylborates containing electronically diverse substituents and hetero-aromatics. The Royal Society of Chemistry 2013.
- Yasu, Yusuke,Koike, Takashi,Akita, Munetaka
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supporting information
p. 2037 - 2039
(2013/03/28)
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- Iron(II)-catalyzed trifluoromethylation of potassium vinyltrifluoroborates
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Exchanging BF3 by CF3: The title reaction proceeds under exceedingly mild reaction conditions and provides 2-arylvinyl- and 2-heteroarylvinyl-substituted substrates with E/Z selectivities of more than 95:5. Experimental observations suggest that the reaction does not proceed through a transmetalation of the RBF3K species to the iron catalyst. Copyright
- Parsons, Andrew T.,Senecal, Todd D.,Buchwald, Stephen L.
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supporting information; experimental part
p. 2947 - 2950
(2012/05/05)
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- A domino approach of heck coupling for the synthesis of β-trifluoromethylstyrenes
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A domino approach of Heck coupling was used to synthesize β-trifluoromethylstyrene derivatives from iodoarenes and 1-iodo-3,3,3-trifluoropropane in moderate to good yields. This method avoids the use of low-boiling, gaseous reagents such as 3,3,3-trifluoropropene, and additives and phosphines in the catalytic system.
- Prakash, G. K. Surya,Krishnan, Hema S.,Jog, Parag V.,Iyer, Anjali P.,Olah, George A.
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supporting information; experimental part
p. 1146 - 1149
(2012/04/04)
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- Efficient trifluoromethylation of activated and non-activated alkenyl halides by using (trifluoromethyl)trimethylsilane
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An efficient method for the trifluoromethylation of halogenated double bonds by using in situ generated "trifluoromethyl copper" is described. Herein, the most common trifluoromethyl source, (trifluoromethyl) trimethylsilane, was converted selectively int
- Hafner, Andreas,Braese, Stefan
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supporting information; experimental part
p. 3044 - 3048
(2012/01/02)
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- A reverse Wittig coupling with trifluoroacetaldehyde: A convenient one-step synthesis of trifluoromethyl alkenes
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A novel, mild synthesis of aryl-3,3,3-trifluoropropenes by Wittig olefmation of benzylphosphonium ylides with in-situ generated trifluoroacetaldehyde is described. The in-situ formed trifluoroacetaldehyde efficiently traps the Wittig ylides and yields tri
- Landge, Shainaz M.,Borkin, Dmitry A.,Toeroek, Bela
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scheme or table
p. 439 - 443
(2010/04/23)
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- Photochemical generation of highly destabilized vinyl cations: The effects of α- and β-trifluoromethyl versus α- and β-methyl substituents
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(Chemical Equation Presented). The photochemical reactions in methanol of the vinylic halides 1-4, halostyrenes with a methyl or a trifluoromethyl substituent at the α- or β-position, have been investigated quantitatively. Next to E/Z isomerization, the reactions are formation of vinyl radicals, leading to reductive dehalogenation products, and formation of vinyl cations, leading to elimination, nucleophilic substitution, and rearrangement products. The vinyl cations are parts of tight ion pairs with halide as the counterion. The elimination products are the result of β-proton loss from the primarily generated α-CH3 and α-CF3 vinyl cations, or from the α-CH3 vinyl cation formed from the β-CH3 vinyl cation via a 1,2-phenyl shift. The β-CF 3 vinyl cation reacts with methanol yielding nucleophilic substitution products, no migration of the phenyl ring producing the α-CF3 vinyl cation occurs. The α-CF3 vinyl cation, which is the most destabilized vinyl cation generated thus far, gives a 1,2-fluorine shift in competition with proton loss. The experimentally derived order of stabilization of the vinyl cations photogenerated in this study, α-CF3 3 3 3, is corroborated by quantum chemical calculations, provided the effect of solvent is taken into account.
- Van Alem, Kaj,Belder, Geerte,Lodder, Gerrit,Zuilhof, Han
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p. 179 - 190
(2007/10/03)
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- Palladium-catalyzed desulfitative mizoroki-heck couplings of sulfonyl chlorides with mono-and disubstituted olefins: Rhodium-catalyzed desulfitative heck-type reactions under phosphine- And base-free conditions
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New conditions have been found for the desulfitative Mizoroki-Heck arylation and trifluoromethylation of mono- and disubustituted olefins with arenesulfonyl and trifluoro-methanesulfonyl chlorides. Thus (E)-1,2- disubstituted alkenes with high ster-eoselectivity and 1,1,2-disubstituted alkenes with 12:1 to 21:1 E/Z steroselectivity can be obtained. Herrmann's palladacycle at 0.1 mol% is sufficient to catalyze these reactions, for which electron-rich or electron-poor sulfonyl chlorides and alkenes are suitable. If phosphine- and base-free conditions are required. 1 mol% [RriCl(C 2,H4)2] catalyzes the desulfitative cross-cou pling reactions. Contrary to results reported for [RuCl2(PPh 3)2]-catalyzed coupling reactions with sulfonyl chlorides, the palladium and rhodium desulfitative Mizoroki-Heck coupling reactions are not inhibited by radical scavenging agents. Possible sulfones arising from the sulfonylation of alkenes at 60°C are not desulfitated at higher temperatures in the presence of the Pd or Rh catalysts.
- Dubbaka, Srinivas Reddy,Vogel, Pierre
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p. 2633 - 2641
(2007/10/03)
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- Synthesis and Reactions of (2,2,2-Trifluoroethyl)triphenylphosphonium Trifluoromethanesulfonate
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(2,2,2-Trifluoroethyl)triphenylphosphonium trifluoromethanesulfonate (triflate) (1) was readily synthesized in high yield from triphenylphosphane and 2,2,2-trifluoroethyl triflate. The Wittig olefination of 1 with aromatic aldehydes bearing electron-withdrawing groups with CsF as a base in DMF proceeded cleanly, producing the corresponding 3,3,3-trifluoropropenylidene compounds in good yields. On the other hand, the hydrolysis of 1 in methanol containing sodium hydroxide gave (2,2-dimethoxyvinyl)triphenylphosphonium triflate (6a) in high yield instead of the corresponding (2,2,2-trifluoroethyl)diphenylphosphane oxide. Furthermore, reactions between 1 and secondary amines exclusively gave the novel (Z)-(2-amino-2-fluorovinyl)triphenylphosphonium triflates (10) in high yields. Wiley-VCH Verlag GmbH & Co KGaA, 69451 Weinheim, Germany, 2003.
- Hanamoto, Takeshi,Morita, Noriko,Shindo, Keiko
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p. 4279 - 4285
(2007/10/03)
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- Convenient synthesis of 3,3,3-trifluoropropenyl compounds from aromatic aldehydes by means of the TBAF-mediated horner reaction
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A simple synthesis of 3,3,3-trifluoropropenyl compounds by means of the TBAF-mediated Horner reaction is described. The reagent, 2,2,2-trifluoroethyldiphenylphosphine oxide, was readily prepared either by Arbuzov reaction of ethyl diphenylphosphinite with 2,2,2-trifluoroethyl iodide or by treating chlorodiphenylphosphine with trifluoroacetic acid and water. Treatment of the phosphine oxide with aromatic aldehydes in the presence of TBAF at room temperature afforded the corresponding 3,3,3-trifluoropropenyl compounds in good yields. The present method is very convenient for preparing 3,3,3-trifluoropropenyl compounds from aromatic aldehydes in terms of availability of the reagent, operational simplicity, and good yields of the products.
- Kobayashi, Tetsuya,Eda, Takuya,Tamura, Osamu,Ishibashi, Hiroyuki
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p. 3156 - 3159
(2007/10/03)
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- A new and improved synthesis of trans-1,2-diiodoalkenes and their stereospecific and highly regioselective trifluoromethylation
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Reaction of terminal alkynes with iodine in the presence of CuI (5%) in acetonitrile under reflux for several hours gave the trans-1,2-diiodoalkenes in high yields. The trifluoromethylation of these diiodides using FSO2CF2CO2Me/CuI/DMF proceeded in excellent yields in a stereospecific and highly regioselective manner.
- Duan, Jianxin,Dolbier Jr., William R.,Chen, Qing-Yun
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p. 9486 - 9489
(2007/10/03)
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- Potassium 3-oxa-ω-fluorosulfonylperfluoropentanoate (FO2SCF2CF2OCF2CO2K), a low-temperature trifluoromethylating agent for organic halides; its α-carbon-oxygen bond fragmentation
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The trifluoromethylation of organic halides with FO2SCF2CF2OCF2CO2K (1) in DMF can be accomplished at 45 °C which is advantageous for thermally sensitive substrates. α-Carbon-oxygen bond fragmentation of 1 and the related β-carbon-oxygen bond scission are discussed.
- Long, Zheng-Yu,Duan, Jian-Xin,Lin, Yuan-Bin,Guo, Cai-Yun,Chen, Qing-Yun
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p. 177 - 181
(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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- Methyl 3-Oxa-ω-fluorosulfonylperfluoropentanoate: a Versatile Trifluoromethylating Agent for Organic Halides
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Methyl 3-oxa-ω-fluorosulfonylperfluoropentanoate FSO2CF2CF2OCF2CO2Me 1, prepared through the reaction of readily available ICF2CF2OCF2CF2SO2F and SO3 followed by MeOH, is a very convenient trifluoromethylating agent; in the presence of copper(I) iodide, 1 not only reacts with vinyl, benzyl allyl, phenyl iodides and bromides, but also with aryl chlorides to give the corresponding trifluoromethyl compounds in moderate to high yield; a probable reaction mechanism is proposed.
- Chen, Qing-Yun,Duan, Jian-Xing
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p. 1389 - 1391
(2007/10/02)
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- A NOVEL AND CONVENIENT METHOD FOR TRIFLUOROMETHYLATION OF ORGANIC HALIDES USING CF3SiR'3/KF/Cu(I) SYSTEM
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Fluoride ion induced cross-coupling reaction of organic halides with trifluoromethyltrialkylsilanes takes place in the presence of Cu(I) salts under mild reaction conditions to give the corresponding trifluoromethylated products in high yields.
- Urata, Hisao,Fuchikami, Takamasa
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- Copper electron-transfer induced trifluoromethylation with methyl fluorosulphonyldifluoroacetate
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Treatment of halogen compounds, RX, with methyl fluorosulfonyldifluoroacetate and copper powder in dimethylformamide for 4 h at 65 - 80 deg C resulted in the corresponding trifluoromethylated products, RCF3, in good yield.In the absence of halogen compounds and at 100 deg C, methyl triflone (CF3SO2CH3) was synthesized readily in the 20 - 30percent yield from the same reaction system.The fact that the reaction was suppressed by oxygen, p-dinitrobenzene or in the darkness suggested that a copper-induced electron-transfer process was involved in this new trifluoromethylating system.
- Chen, Qing-Yun,Yang, Guo-Ying,Wu Sheng-Wen
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p. 291 - 298
(2007/10/02)
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- METHYL CHLORODIFLUOROACETATE. A CONVENIENT TRIFLUOROMETHYLATING AGENT
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Treatment of methyl chlorodifluoroacetate with organic halides in the presence of KF and CuI at 100-120 deg C for 7-8 h in DMF gave the corresponding trifluoromethylated derivatives in moderate to high yields.
- Su, De-Bao,Duan, Jian-Xing,Chen, Quing-Yun
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p. 7689 - 7690
(2007/10/02)
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- Electroreductive coupling of halofluoro compounds with aldehydes
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Electroreductive intermolecular coupling of halofluoro compounds such as 1,1,1-trichloro-2,2,2-trifluoroethane, methyl chlorodifluoroacetate, and perfluoroalkyl halides with aldehydes took place effectively in the presence of chlorotrimethylsilane and one of the coupling products, 2,2-dichloro-3,3,3-trifluoro-1-phenyl-1-propranol, was selectively convertible to a variety of compounds with using the electroreduction as a key reaction.
- Shono,Kise,Oka
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p. 6567 - 6570
(2007/10/02)
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- Synthesis of 2,2,2-Trifluoroethylated Onium Salts of Nitrogen, Sulfur, and Phosphorus with (2,2,2-Trifluoroethyl)phenyliodonium Triflate
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Various 2,2,2-trifluoroethyl onium triflates were synthesized by treating tertiary amines, pyridines, quinoline, a triazole, sulfides, and a phosphine with (2,2,2-trifluoroethyl)phenyliodonium triflate.Sulfoxides and N-oxide were converted to the correspo
- Umemoto, Teruo,Gotoh, Yoshihiko
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p. 2008 - 2010
(2007/10/02)
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- Novel Perfluoroalkylation of Alkenes with Perfluoroalkanesulphonyl Chlorides Catalysed by a Ruthenium(II) Complex
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The perfluoroalkylation of acyclic and cyclic alkenes by perfluoroalkanesulphonyl chlorides 1 has been investigated in the presence of a ruthenium(II) catalyst.The addition reactions proceeded smoothly, with extrusion of sulphur dioxide, in alkenes posses
- Kamigata, Nobumasa,Fukushima, Takamasa,Terakawa, Yoshie,Yoshida, Masato,Sawada, Hideo
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p. 627 - 633
(2007/10/02)
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- Methyl Fluorosulphonyldifluoroacetate; a New Trifluoromethylating Agent
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Methyl fluorosulphonyldifluoroacetate, in the presence of copper(I) iodide, is used as the source of trifluoromethyl group which replaces the halogen in aryl, alkenyl, and alkyl halides.
- Chen, Qing-Yun,Wu, Sheng-Wen
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p. 705 - 706
(2007/10/02)
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- Sodium Perfluoroalkane Carboxylates as Sources of Perfluoroalkyl Groups
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Sodium trifluoroacetate, in the presence of copper(I) iodide, is used as a source of trifluoromethyl to replace halogen by trifluoromethyl in benzenoid and heterocyclic aromatic systems, as well as in alkenyl and alkyl halogen compounds.The mechanism of this interesting copper-assisted process has been explored and an intermediate of the form - is proposed.Introduction of higher perfluoroalkyl groups from their respective sodium perfluoroalkane carboxylates has been demonstrated and the machanistic features are compared with those of the trifluoromethylation process.
- Carr, Gillian E.,Chambers, Richard D.,Holmes, Thomas F.,Parker, David G.
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p. 921 - 926
(2007/10/02)
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- A FACILE PREPARATION OF 1-PERFLUOROALKYLALKENES AND ALKYNES. PALLADIUM CATALYZED REACTION OF PERFLUOROALKYL IODIDES WITH ORGANOTIN COMPOUNDS
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Alkenyl, allyl, and alkynylstannanes react with perfluoroalkyl iodides in the presence of a catalytic amount of Pd(PPh3)4 to give alkenes and alkynes bearing perfluoroalkyl group.
- Matsubara, Seijiro,Mitani, Makoto,Utimoto, Kiitiro
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p. 5857 - 5860
(2007/10/02)
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- Ultrasound-Promoted Selective Perfluoroalkylation on the Desired Position of Organic Molecules
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Perfluoroalkylzinc iodides or bromides wich were prepared from perfluoroalkyl iodides or bromides and zinc powder in N,N-dimethylformamide or tetrahydrofuran with ultrasonic irradiation were found to behave as potential perfluoroalkylating reagents for the preparation of a wide variety of perfluoroalkylated compounds.Especially, the ultrasound-promoted asymmetric induction with perfluoroalkyl group on the asymmetrical carbon was achieved by the reaction of perfluoroalkyl halides with optically active enamines in the presence of zinc powder and a catalytic amount of dichlorobis(?-cyclopentadienyl)titanium.
- Kitazume, Tomoya,Ishikawa, Nobuo
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p. 5186 - 5191
(2007/10/02)
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