RESUMO
The preparation of a well-defined trifluoromethylated argentate nBu4N+[Ag(CF3)2]- 1 from fluoroform was described. The complex was stable in the solid state and in solution under an inert atmosphere. Treatment of a variety of (hetero)aryl diazonium tetrafluoroborates with nBu4N+[Ag(CF3)2]- 1 generated trifluoromethylated (hetero)arenes in good to excellent yields. Preliminary experiments were conducted, and a reasonable mechanism of the reaction was proposed.
RESUMO
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.
RESUMO
The synthesis, characterization, and C(sp2 )-CF3 reductive elimination of stable aryl[tris(trifluoromethyl)]cuprate(III) complexes [nBu4 N][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.
RESUMO
A structurally simple, highly reactive chlorinating reagent, N-chloro-N-fluorobenzenesulfonylamine (CFBSA), was conveniently prepared from inexpensive Chloramine B in high yield. A wide range of substrates were chlorinated with it to obtain products in good to high yields and appropriate selectivity.
Assuntos
Cloro/química , Indicadores e Reagentes/químicaRESUMO
A novel and practical reaction for the direct intramolecular oxidative coupling of butenylated arenes is reported. With the catalysis of Pd(OAc)2, reactions of various butenylated arenes and carboxylic acids with Selectfluor reagent in CH3CN solution afforded the corresponding monocarboxylation/cyclization products in good yields under mild conditions. This research demonstrated an economic method with the synthesis of 2-tetralyl carboxylic esters, a valuable class of bioactive compounds.