Palladium-Catalyzed Oxidative Aryltrifluoromethylation of Activated Alkenes at Room Temperature

Abstract

A palladium-catalyzed intramolecular oxidative aryltrifluoromethylation reaction of activated alkenes has been explored. The reaction allows for an efficient synthesis of a variety of CF(3)-containing oxindoles. Preliminary mechanistic study indicated that the reaction involves a C(sp(3))-Pd(IV)(CF(3)) intermediate, which undergoes reductive elimination to afford a C(sp(3))-CF(3) bond.

Photocatalytic fluoroalkylation reactions of organic compounds

“…Trifluoromethylation has, in the past, relied on the use of transition metal catalysts, such as those containing Pd [22][23][24][25][26][27][28][29][30][31][32] and Cu [33][34][35][36][37][38][39][40][41][42][43][44][45][46] . Photoredox catalytic trifluoromethylation, fluoroalkylation and fluorination reactions provide a promising alternative to these existing methods, as it utilizes the environmentally benign protocols that rely on visible light or even sunlight irradiation.…”

Palladium-Mediated Organofluorine Chemistry

“…18,80,83 Ritter has proved that the product of oxidation of palladium(II) acetate complexes with PhI(OAc) 2 is, in fact, a palladium(III) dimer (Scheme 49, a), and that the reductive elimination of aryl acetates takes place easier from a Pd(III) than from a Pd(IV) intermediates. 171 Thus, the formation of palladium(III) dimeric complexes provides a low energy pathway in redox processes involving the formation of C-X bonds.…”

“…a C-C bond formation via reductive elimination). There are several catalytic processes in which this step plays a role, 38,83 such as the Stille and the Negishi cross-couplings, and also coupling reactions involving silicon and copper trifluoromethyl reagents.…”

(Trifluoromethyl)trimethylsilane

“…16 The desired products were obtained via initial arylpalladation of alkenes, continued by sequential oxidation and reductive elimination of Csp 2 Pd IV CF 3 species.…”