82203-84-7Relevant articles and documents
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.
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.
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.
