1680206-12-5Relevant articles and documents
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.
C(sp3)-CF3Reductive Elimination from a Five-Coordinate Neutral Copper(III) Complex
Liu, Shuanshuan,Liu, Shuanshuan,Liu, He,Liu, Shihan,Lu, Zehai,Lu, Changhui,Leng, Xuebing,Lan, Yu,Shen, Qilong
supporting information, p. 9785 - 9791 (2020/07/10)
The reductive elimination from a high-valent late-transition-metal complex for the formation of a carbon-carbon or carbon-heteroatom bond represents a fundamental product-forming step in a number of catalytic processes. While reductive eliminations from well-defined Pt(IV), Pd(IV), Ni(III)/Ni(IV), and Au(III) complexes have been studied, the analogous reactions from neutral Cu(III) complexes remain largely unexplored. Herein, we report the isolation of a stable, five-coordinate, neutral square pyramidal Cu(III) complex that gives CH3-CF3 in quantitative yield via reductive elimination. Mechanistic studies suggest that the reaction occurs through a synchronous bond-breaking/bond-forming process via a three-membered ring transition state.
Synthesis method of prodrug for Mycobacterium tuberculosis activity inhibitor
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Paragraph 0014; 0019-0021, (2019/10/23)
The invention provides a synthesis method of a prodrug for a Mycobacterium tuberculosis activity inhibitor. The method comprises the following steps: S1, adding acetic acid into a reactor A, sequentially adding cuprous chloride, bipyridine, trifluoromethyltrimethylsilane and potassium fluoride, carrying out a reaction, filtering the obtained solution to obtain a bright yellow solid, washing the bright yellow solid, and carrying out suction drying to obtain a bipyridine complex of trifluoromethy copper; and S2, adding the bipyridine complex of trifluoromethy copper, obtained in step S1, and a piperidine derivative into a reactor B, then adding triethylsilane, potassium persulfate, acetone and deionized water, carrying out a reaction at room temperature, carrying out reduced pressure rotaryevaporation to remove the solvent, washing the obtained crude product, concentrating the washed crude product, and recrystallizing the concentrated crude product to obtain the target product. The method has the advantages of low price and easy obtaining of raw materials, simplicity in reaction operation, obtaining of the trifluoromethyl product with high added values, realization of complete separation only by recrystallization, realization of the purity of the final product being 98% or above, and realization of amplified production by using water as a green solvent in the reaction and avoiding anhydrous and anaerobic harsh conditions.
A Key Intermediate in Copper-Mediated Arene Trifluoromethylation, [nBu4N][Cu(Ar)(CF3)3]: Synthesis, Characterization, and C(sp2)?CF3 Reductive Elimination
Lu, Zehai,Liu, He,Liu, Shihan,Leng, Xuebing,Lan, Yu,Shen, Qilong
supporting information, p. 8510 - 8514 (2019/05/22)
The synthesis, characterization, and C(sp2)?CF3 reductive elimination of stable aryl[tris(trifluoromethyl)]cuprate(III) complexes [nBu4N][Cu(Ar)(CF3)3] are described. Mechanistic investigations, including kinetic studies, studies of the effect of temperature, solvent, and the para substituent of the aryl group, as well as DFT calculations, suggest that the C(sp2)?CF3 reductive elimination proceeds through a concerted carbon–carbon bond-forming pathway.
Copper-Mediated Trifluoromethylation of Benzylic Csp3?H Bonds
Paeth, Matthew,Carson, William,Luo, Jheng-Hua,Tierney, David,Cao, Zhi,Cheng, Mu-Jeng,Liu, Wei
supporting information, p. 11559 - 11563 (2018/07/31)
Trifluoromethyl-containing compounds play a significant role in medicinal chemistry, materials and fine chemistry. Although direct C?H trifluoromethylation has been achieved on Csp2?H bonds, direct conversion of Csp3?H bonds to Csp3?CF3 remains challenging. We report herein an efficient protocol for the selective trifluoromethylation of benzylic C?H bonds. This process is mediated by a combination CuIII?CF3 species and persulfate salts. A wide range of methylarenes can be selectively trifluoromethylated at the benzylic positions. A combination of experimental and theoretical mechanistic studies suggests that the reaction involves a radical intermediate and a CuIII?CF3 species as the CF3 transfer reagent.
Isolation and characterization of copper(III) trifluoromethyl complexes and reactivity studies of aerobic trifluoromethylation of arylboronic acids
Zhang, Song-Lin,Bie, Wen-Feng
, p. 70902 - 70906 (2016/08/05)
The isolation, characterization and reactivity of transition metal trifluoromethyl complexes are fundamental and challenging topics in trifluoromethylation chemistry. We report herein the synthesis and isolation of two new complexes [(phen)CuI(PPh3)2]+[CuIII(CF3)4]- (2) and (phen)CuIII(CF3)3 (3) as well as a known complex (bpy)CuIII(CF3)3 (4) at room temperature. 2 and 3 have been fully characterized using 1H, 19F, 31P NMR, elemental analyses and X-ray crystallography. Reactivity studies indicate that 2 is unreactive toward arylboronic acids. In contrast, 3 and 4 can react with various aryl and heteroaryl boronic acids to deliver trifluoromethylated arenes in good to quantitative yields under mild conditions. The presence of a fluoride additive in DMF under aerobic conditions is crucial to these reactions. This study provides fundamental information about the structure and reactivity of elusive Cu(iii) trifluoromethyl complexes that have been proposed as relevant reactive intermediates in many trifluoromethylation reactions.
Distinct mechanism of oxidative trifluoromethylation with a well-defined Cu(II) fluoride promoter: Hidden catalysis
Nebra, Noel,Grushin, Vladimir V.
supporting information, p. 16998 - 17001 (2015/02/18)
The fluoride [(bpy)CuF2(H2O)]·2H2O (1) reacts with CF3SiMe3 and PhB(OH)2 in DMF at rt to give PhCF3 in >95% yield within 15 min. Although 1 is a Cu(II) complex, this reaction occ
