Cooperative Effect of Silver in Copper-Catalyzed Trifluoromethylation of Aryl Iodides Using Me₃SiCF₃

Abstract

An effective model of cooperative effect of silver for the coppercatalyzed trifluoromethylation of activated and unactivated aryl iodides to trifluoromethylated arenes using Me 3 SiCF 3 was achieved with a broad substrate scope.

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

“…Our design of a cooperative dual Pd/Ag bimetallic catalyst [23][24][25][26][27][28] for direct difluoromethylation of aryl halides was inspired by a classical cross-coupling reaction-Sonogashira reaction 29 . It was proposed that the palladium-catalysed alkynylation of aryl halides was catalysed by a two-component catalyst system consisting of two different transition metal complexes (Pd/Cu), in which the palladium-catalysed activation of aryl halides was cooperatively coupled through a transmetalation process with the catalytic route of in situ formation cuprous acetylides in the presence of an amine.…”

Silver Compounds in Synthetic Chemistry. Part 8. Complexes of Perfluoroorgano Silver(I) Derivatives with 4‐Dimethylaminopyridine (DMAP)

“…This decomposition product was unambiguously characterized on the basis of NMR spectroscopic methods ( 1 H, 19 F, 13 C, and correlation techniques). While the proton signal is split into a quartet caused by a 6 J(H,F) (or through space [31] ) interaction of less than 1 Hz, the 19 F signal occurs only broadened (Δ 1/2 ≈ 6 Hz).…”

“…[2,3,8,9] Also in the field of organic synthesis, perfluoroorgano silver compounds attract more and more attention in the conversion of acid chlorides into perfluoroorgano ketones, [10,11] in the copper-mediated trifluoromethylation of aryl halides, [12,13] in C-H fluoroalkylation of differently substituted aromatic substrates, [14][15][16] or in the conversion of diazonium salts into trifluoromethyl-substituted aromatics. [17] Earlier studies [18] revealed that in solution especially perfluoroalkylsilver derivatives undergo complex exchange equilibria involving a "neutral" species, AgR f , an "ionic" species, Ag[Ag(R f ) 2 ], and a "polymeric" form, [ 4-Dimethylaminopyridine (DMAP), additionally to its excellent catalytic activity in organic transformations, [19] exhibits positive features making among many other metal compounds silver derivatives easily crystallizable.…”

Investigations into Transition-Metal-Catalyzed Arene Trifluoromethylation Reactions

“…Third, AgCF 3 is readily synthetically accessible (although its reactivity with organic substrates had not previously been explored extensively). 20 …”

“…For example, several reports have shown that Ag salts serve as promoters for the Cu-catalyzed trifluoromethylation of aryl iodides. 20b,31 The role of Ag has been proposed to involve mediating transmetalation of CF 3 − from Si (in TMSCF 3 ) to Cu. 17b However, the current results (along with those in Part 2 of this Account) suggest that the role of Ag may be to generate CF 3 • in these transformations.…”