Palladium-Catalyzed C–H Perfluoroalkylation of Arenes

Abstract

A new Pd-catalyzed reaction for the coupling between perfluoroalkyl iodides (R(F)I) and simple aromatic substrates is described. The perfluoroalkylated arene products are obtained in good to excellent yields in the presence of a phosphine-ligated Pd catalyst and Cs(2)CO(3) as a base. The development, optimization, scope, and preliminary mechanistic studies of these transformations are reported.

Palladium catalyzed direct α-arylation of α,α-difluoroketones with aryl bromides

“…Monodentate ligands and bidentate ligands showed similar catalytic efficiencies as SPhos and XPhos in the a-arylation reactions (entries [12][13][14][15][16], although they could promote the reductive elimination of fluoroalkyl palladium(II) intermediates [22]. To our delight, when BINAP [23] was used as the ligand, the desired product 2a was formed in 90% yield with full conversion of 1 (entry 17). When the arylation was carried out at 100 8C, both the conversion of 1 and yield of 2a were decreased (entry 18).…”

A General Strategy for the Perfluoroalkylation of Arenes and Arylbromides by Using Arylboronate Esters and [(phen)CuRF]

“…[1b] However, methods to prepare perfluoroalkyl arenes are limited because they cannot be prepared by halogenation of the corresponding alkylarene. [ 3c,11] Fortunately, perfluoroalkyl analogs of [(phen)-CuCF 3 ], such as [(phen)CuCF 2 CF 3 ] and [(phen)-CuCF 2 CF 2 CF 3 ], are easily prepared. [7] These reagents react with arylboronate esters in a fashion similar to that of [(phen)CuCF 3 ], giving perfluoroalkyl arenes in good yields.…”

Solution-phase perfluoroalkylation of C60 leads to efficient and selective synthesis of bis-perfluoroalkylated fullerenes

“…[41] Substitution of aromatic hydrogen atoms by R F · radicals has been used to prepare aromatic compounds bearing various R F groups[42–46] (see also [47,48] for similar catalytic processes); addition of R F · radicals to alkenes has also been well-studied. [49,50] Thermolysis of R F I or (R F CO 2 ) 2 precursors has been commonly used to generate R F · radicals (see for example [42,43,46]).…”