1409976-31-3Relevant articles and documents
Development and Mechanistic Investigations of a Base-Free Suzuki-Miyaura Cross-Coupling of α,α-Difluoroacetamides via C-N Bond Cleavage
Amgoune, Abderrahmane,Bouyssi, Didier,Jeanneau, Erwann,Krachko, Tetiana,Monteiro, Nuno,Onida, Killian,Reina, Antonio
, p. 2189 - 2197 (2020)
This study describes the development and understanding of a palladium-catalyzed cross-coupling of fluoroacetamides with boronic acids, under base-free conditions, to selectively give valuable α,α-difluoroketone derivatives. Detailed mechanistic studies were conducted to assess the feasibility of each elementary step, that is, C(acyl)-N bond oxidative addition, followed by base-free transmetallation and reductive elimination. These investigations allowed the structural characterization of palladium(II)fluoroacyl intermediates derived from C-N bond oxidative addition of an amide electrophile. They also revealed the high reactivity of these intermediates for transmetallation with boronic acids without exogenous base. The mechanistic studies also provided a platform to design a practical catalytic protocol for the synthesis of a diversity of α,α-difluoroketones, including CF2H-ketones. Finally, the synthetic potential of this fluoroacylation methodology is highlighted in sequential, orthogonal C-Br and C-N bond functionalization of an α-bromo-α,α-difluoroacetamide with a focus on compounds of potential biological relevance.
Palladium catalyzed direct α-arylation of α,α- difluoroketones with aryl bromides
Guo, Chen,Wang, Ruo-Wen,Qing, Feng-Ling
, p. 135 - 142,8 (2020/08/20)
The palladium-catalyzed direct α-arylations of α,α- difluoroketones with diverse aryl bromides have been developed by using rac-BINAP as ligand and Cs2CO3 as a mild base in xylene. This method provides an efficient and straightforward access to a variety of α-aryl-α,α-difluoroketones with broad substrate scope.
