21249-93-4Relevant academic research and scientific papers
Active trifluoromethylating agents from well-defined copper(I)-CF 3 complexes
Dubinina, Galyna G.,Furutachi, Hideki,Vicic, David A.
, p. 8600 - 8601 (2008)
The first examples of isolable and structurally characterized Cu(I)-CF3 complexes are reported. N-Heterocyclic carbene (NHC)-supported copper tert-butoxide complexes reacted with Me3Si-CF3 to afford new (NHC)Cu-CF3 complexes whose structures were dependent on whether or not the C4-C5 positions of the five-membered NHC rings were saturated. In situ generated (SIiPr)Cu-CF3 cleanly transferred its trifluoromethyl group to a number of organic halides under mild conditions. Copyright
Simple, stable, and easily accessible well-defined CuCF3 aromatic trifluoromethylating agents
Tomashenko, Olesya A.,Escudero-Adan, Eduardo C.,Martinez Belmonte, Marta,Grushin, Vladimir V.
, p. 7655 - 7659 (2011)
Give me an F: Exceptionally easy to make in over 90 yield (see scheme) and air-stable in the solid state, [(Ph3P)3Cu(CF3)] is a remarkable example of a rarely encountered well-defined Cu(I) trifluoromethylating agent and a convenient starting material for the synthesis of other CuCF3 complexes, such as [(phen)Cu(PPh3)(CF 3)]. Copyright
Using Chlorotrifluoroethane for Trifluoroethylation of (Hetero)aryl Bromides and Chlorides via Nickel Catalysis
Li, Xuefei,Gao, Xing,He, Chun-Yang,Zhang, Xingang
supporting information, p. 1400 - 1405 (2021/02/20)
A nickel-catalyzed reductive cross-coupling between industrial chemical CF3CH2Cl and (hetero)aryl bromides and chlorides has been reported. The reaction is synthetically simple without the preparation of arylmetals and exhibits high functional group tolerance. The utility of this protocol has been demonstrated by the late-stage modification of pharmaceuticals, providing a facile route for medicinal chemistry.
Direct C(sp3)?H Trifluoromethylation of Unactivated Alkanes Enabled by Multifunctional Trifluoromethyl Copper Complexes
Choi, Geunho,Lee, Geun Seok,Park, Beomsoon,Kim, Dongwook,Hong, Soon Hyeok
supporting information, p. 5467 - 5474 (2021/01/20)
A mild and operationally simple C(sp3)?H trifluoromethylation method was developed for unactivated alkanes by utilizing a bench-stable CuIII complex, bpyCu(CF3)3, as the initiator of the visible-light photoinduced reaction, the source of a trifluoromethyl radical as a hydrogen atom transfer reagent, and the source of a trifluoromethyl anion for functionalization. The reaction was initiated by the generation of reactive electrophilic carbon-centered CF3 radical through photoinduced homolytic cleavage of bpyCu(CF3)3, followed by hydrogen abstraction from an unactivated C(sp3)?H bond. Comprehensive mechanistic investigations based on a combination of experimental and computational methods suggested that C?CF3 bond formation was enabled by radical–polar crossover and ionic coupling between the resulting carbocation intermediate and the anionic CF3 source. The methylene-selective reaction can be applied to the direct, late-stage trifluoromethylation of natural products and bioactive molecules.
Preparation method of trifluoroethyl compounds
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Paragraph 0052; 0053; 0054; 0055; 0056; 0057; 0058, (2020/01/25)
The invention discloses a preparation method of trifluoroethyl compounds. The trifluoroethyl compounds are synthesized by directly using cheap and abundant industrial raw materials 2-chloro-1,1,1-trifluoroethane and halogenated substances as raw materials by stirring in a polar solvent under the action of a catalytic system using cheap and an easily available alkali metal nickel salt catalyst anda pyridine ligand for reacting under mild reaction conditions of 50-90 DEG C for 12-24 hours, and the efficient introduction of the trifluoroethyl groups to aromatic ring groups or heterocyclic aryl groups can be realized to prepare the trifluoroethyl compounds. The method has the advantages of mild reaction conditions, simple operation, low cost of raw materials and catalysts, good compatibilityof substrate functional groups, easy expansion of reaction scale, simple separation of products and suitability for industrial production.
Metal-Free Construction of the C(sp3)-CF3 Bond: Trifluoromethylation of Hydrazones with Togni's Reagent under Mild Conditions
Zeng, Huiying,Luo, Zhen,Han, Xinlong,Li, Chao-Jun
, p. 5948 - 5951 (2019/08/29)
A metal-free trifluoromethylation of hydrazones with Togni's reagent under mild conditions was developed. Various functional groups including ester, methoxy, dimethoxy, nitro, halogen, and heterocyclic compounds were tolerated. This simple and green strategy provides a practical tool to construct C(sp3)-CF3 bonds.
Denitrogenative Hydrotrifluoromethylation of Benzaldehyde Hydrazones: Synthesis of (2,2,2-Trifluoroethyl)arenes
Zhao, Zhensheng,Ma, Kevin C. Y.,Legault, Claude Y.,Murphy, Graham K.
supporting information, p. 11240 - 11245 (2019/08/20)
Reacting hydrazones of arylaldehydes with Togni's CF3-benziodoxolone reagent, in the presence of potassium hydroxide and cesium fluoride, induces a denitrogenative hydrotrifluoromethylation event to produce (2,2,2-trifluoroethyl)arenes. This novel reaction was tolerant to many electronically-diverse functional groups and substitution patterns, as well as naphthyl- and heteroaryl-derived substrates. Advantages of this process include the easy access to hydrazone precursors on a large scale, speed and operational simplicity, and being transition metal-free.
Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes
Paeth, Matthew,Tyndall, Sam B.,Chen, Liang-Yu,Hong, Jia-Cheng,Carson, William P.,Liu, Xingwu,Sun, Xiaodong,Liu, Jinjia,Yang, Kundi,Hale, Elizabeth M.,Tierney, David L.,Liu, Bin,Cao, Zhi,Cheng, Mu-Jeng,Goddard, William A.,Liu, Wei
supporting information, p. 3153 - 3159 (2019/03/06)
Carbon-carbon bond-forming reductive elimination from elusive organocopper(III) complexes has been considered the key step in many copper-catalyzed and organocuprate reactions. However, organocopper(III) complexes with well-defined structures that can undergo reductive elimination are extremely rare, especially for the formation of Csp3-Csp3 bonds. We report herein a general method for the synthesis of a series of [alkyl-CuIII-(CF3)3]- complexes, the structures of which have been unequivocally characterized by NMR spectroscopy, mass spectrometry, and X-ray crystal diffraction. At elevated temperature, these complexes undergo reductive elimination following first-order kinetics, forming alkyl-CF3 products with good yields (up to 91%). Both kinetic studies and DFT calculations indicate that the reductive elimination to form Csp3-CF3 bonds proceeds through a concerted transition state, with a ΔH? = 20 kcal/mol barrier.
Copper-Catalyzed Trifluoromethylation of Alkyl Bromides
Kornfilt, David J.P.,Macmillan, David W.C.
supporting information, p. 6853 - 6858 (2019/05/10)
Copper oxidative addition into organohalides is a challenging two-electron process. In contrast, formal oxidative addition of copper to C sp2 carbon-bromine bonds can be accomplished by employing latent silyl radicals under photoredox conditions. This novel paradigm for copper oxidative addition has now been applied to a Cu-catalyzed cross-coupling of C sp3-bromides. Specifically, a copper/photoredox dual catalytic system for the coupling of alkyl bromides with trifluoromethyl groups is presented. This operationally simple and robust protocol successfully converts a variety of alkyl, allyl, benzyl, and heterobenzyl bromides into the corresponding alkyl trifluoromethanes.
Exploring the Role of Coinage Metalates in Trifluoromethylation: A Combined Experimental and Theoretical Study
Martínez de Salinas, Sara,Mudarra, ángel L.,Odena, Carlota,Martínez Belmonte, Marta,Benet-Buchholz, Jordi,Maseras, Feliu,Pérez-Temprano, Mónica H.
supporting information, p. 9390 - 9394 (2019/04/03)
Despite the known nucleophilic nature of [M(CF3)2]? (M=Cu, Ag, Au) complexes, their participation in trifluoromethylation reactions of aryl halides remains unexplored. Here, for the first time, selective access to a [Cu(CF3)2]? species is reported, which is ubiquitous in Cu-mediated trifluoromethylations, and we rationalize its complex mechanistic scenario as well as its behavior compared to its silver and gold congeners through a combination of experimental and computational approaches.
