82203-84-7Relevant academic research and scientific papers
Hydrogen-Bonding-Assisted α-F Elimination from Cu-CF3 for in Situ Generation of R3N·HF Reagents: Reaction Design and Applications
Zhang, Song-Lin,Dong, Jia-Jia
, p. 6893 - 6896 (2019)
We report herein a strategy of ammonium hydrogen-bonding-assisted α-F elimination from Cu-CF3 compounds that generates R3N·HF reagents in situ. Combining this strategy and Cu(III)-CF3 chemistry with alkynes, dual fluorination and trifluoromethylation of terminal alkynes is enabled by a single Cu(III)-CF3 compound assisted by a tertiary amine with excellent regio- and stereoselectivity. This strategy also enables the development of other reaction types involving trapping of the in situ-formed R3N·HF reagents by other electrophilic groups and can be used for the late-stage functionalization of estrone derivatives.
General and selective syn -carboxylation-trifluoromethylation of terminal alkynes: Application to the late-stage modification of dehydrocholic acid
Zhang, Song-Lin,Xiao, Chang,Wan, Hai-Xing,Zhang, Xiaoming
, p. 4099 - 4102 (2019/04/30)
A general and selective method is developed that allows difunctionalization of terminal alkynes by a Cu(iii)-CF3 complex and a carboxylic acid regioselectively and with unusual syn-stereochemistry. This method is broadly applicable to various carboxylic acids and terminal alkynes, producing a range of biologically active trifluoromethyl enol carboxylic esters. The synthetic potential of this method is further demonstrated by the late-stage functionalization of a complex pharmaceutical compound dehydrocholic acid.
Cu(III)-CF3 Complex Enabled Unusual (Z)-Selective Hydro-trifluoromethylation of Terminal Alkynes
Zhang, Song-Lin,Xiao, Chang
, p. 10908 - 10915 (2018/09/06)
An efficient and selective hydro-trifluoromethylation of terminal alkynes is developed to enable the synthesis of 1,2-disubstituted trifluoromethylated Z-alkenes from terminal alkynes, a silane and a Cu(III)-CF3 complex in DMF. The unusual Z-selectivity and the compatibility of various functional groups make this reaction complementary to previous vinyl-CF3 bond-forming methods producing dominantly E-products or a mixture of E,Z-isomers. Extensive mechanistic studies indicate that this reaction may involve a key step of migratory insertion of initially formed Ar-C-C-CF3 into LCu(I)-H intermediate and subsequent hydrogenation of the vinyl-copper species to give finally the Z-trifluoromethylated styrenes. Deuterium labeling experiments show that DMF acts not merely as the solvent but also as the source of α-H in the Z-trifluoromethylated styrene products. Given the novel syn-difunctionalization of alkynes using Cu(III)-CF3 complexes/a nucleophilic reagent we developed recently that are also in contrast to the previous anti-difunctionalization chemistry, Cu(III)-CF3 complexes are demonstrated to show distinct reactivity properties compared to conventional CF3 reagents (Togni's reagents and Umemoto-type reagents) and may thus enable the development of other interesting reactions.
Diverse copper(iii) trifluoromethyl complexes with mono-, bi- and tridentate ligands and their versatile reactivity
Zhang, Song-Lin,Xiao, Chang,Wan, Hai-Xing
supporting information, p. 4779 - 4784 (2018/04/11)
Cu(iii) trifluoromethyl complexes are proposed as essential intermediates for many copper-promoted trifluoromethylation reactions, but remain elusive and scarcely explored. We report herein the isolation and spectroscopic and X-ray crystallographic charac
Cu(I)/Ag(I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3at room temperature
Yang, Lingling,Jiang, Linlin,Li, Yaming,Fu, Xinmei,Zhang, Rong,Jin, Kun,Duan, Chunying
, p. 3858 - 3862 (2016/07/06)
A novel Cu(I)/Ag(I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3has been developed for the construction of Csp-CF3bond under mild conditions. This method proceeds smoothly at room temperature and shows a widely functional compatibility, providing a series of corresponding trifluoromethylated acetylenyl-containing aromatics in good yields.
Copper-mediated trifluoromethylation using phenyl trifluoromethyl sulfoxide
Li, Xinjin,Zhao, Jingwei,Zhang, Liang,Hu, Mingyou,Wang, Limin,Hu, Jinbo
supporting information, p. 298 - 301 (2015/03/04)
A new method for the generation of trifluoromethylcopper ( CuCF3 ) species from readily available phenyl trifluoromethyl sulfoxide has been developed. The CuCF3 reagent can be applied in efficient trifluoromethylations of aryl iodides and activated aryl bromides in the absence of additional ligands. Furthermore, the CuCF3 species can also undergo oxidative cross-coupling with terminal alkynes and arylboronic acids.
Synthesis of 3-trifluoromethylbenzofurans via palladium-catalyzed tandem elimination/annulation of β-chloro-β-(trifluoromethyl)styrenes with 2-halophenols
Wang, Chong,Chen, Lian-Hui,Deng, Chen-Liang,Zhang, Xing-Guo
, p. 313 - 319 (2014/02/14)
A palladium-catalyzed tandem elimination and annulation reaction has been developed. In this way, a variety of 3-trifluoromethybenzofurans were prepared in moderate to good yields via tandem reaction of β-chloro-β- (trifluoromethyl)styrenes with 2-iodophe
Practical methods for the synthesis of trifluoromethylated alkynes: Oxidative trifluoromethylation of copper acetylides and alkynes
Tresse, Cedric,Guissart, Celine,Schweizer, Stephane,Bouhoute, Yassine,Chany, Anne-Caroline,Goddard, Mary-Lorene,Blanchard, Nicolas,Evano, Gwilherm
supporting information, p. 2051 - 2060 (2014/07/07)
Two practical and complementary methods are reported for the synthesis of trifluoromethylated alkynes. The first one, a mix-and-stir process, is based on the oxidative trifluoromethylation of readily available and bench-stable copper acetylides while the second one, which displays a broad substrate scope and has several advantages over existing procedures, is based on the oxidative copper-catalyzed direct trifluoromethylation of terminal alkynes. Both reactions provide user-friendly processes for the synthesis of trifluoromethylated acetylenes which can be easily obtained from readily available starting materials.
Fragmentation of trifluoromethylated alkenes and acetylenes by N, N -binucleophiles. Synthesis of imidazolines or imidazolidines (Oxazolidines) controlled by substituent
Nenajdenko, Valentine G.,Muzalevskiy, Vasiliy M.,Shastin, Aleksey V.,Balenkova, Elizabeth S.,Kondrashov, Evgeniy V.,Ushakov, Igor A.,Rulev, Alexander Yu.
supporting information; experimental part, p. 5679 - 5688 (2010/11/19)
The reaction of β-halogeno-β-polyfluoromethylstyrenes with N,N- or N,O-binucleophiles leads to unexpected fragmentation products (imidazolines) or to heterocyclization giving CF3-substituted imidazolidines (N,N-) and oxazolidines (N,O-) depending on aryl substituent. The scope and the reaction mechanism are discussed.
Synthetic approach to alkoxy-β-(trifluoromethyl)styrenes and their application in the synthesis of new trifluoromethylated heterocycles
Muzalevskiy, Vasiliy M.,Nenajdenko, Valentine G.,Shastin, Aleksey V.,Balenkova, Elizabeth S.,Haufe, Guenter
experimental part, p. 2249 - 2259 (2009/12/27)
A new convenient stereoselective pathway to alkoxy-β-(trifluoromethyl) styrenes is described. Reactions of β-chloro- and β-bromo-β- (trifluoromethyl)styrenes with sodium methoxide and potassium tert-butoxide led to methoxy- and tert-butoxy-β-(trifluoromethyl) styrenes in good to excellent yields. Bromination of tert-butoxy-β-(trifluoromethyl)styrenes proceeded with formation of aryl(bromo)methyl trifluoromethyl ketones. The latter compounds were found to be useful starting materials for the synthesis of different heterocyclic compounds bearing a trifluoromethyl group. In this way trifluoromethylated derivatives of imidazopyridine, imidazopyrimidine, imidazobenzimidazole, imidazothiazole, thiazole, and aminothiazole were obtained in moderate to high yield. Georg Thieme Verlag Stuttgart.
