1409976-27-7Relevant academic research and scientific papers
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 (2020/02/28)
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.
Pd-catalyzed α-arylation of α,α-difluoroketones with aryl bromides and chlorides. A route to difluoromethylarenes
Ge, Shaozhong,Cha?adaj, Wojciech,Hartwig, John F.
supporting information, p. 4149 - 4152 (2014/04/03)
We report the Pd-catalyzed α-arylation of α,α- difluoroketones with aryl and heteroaryl bromides and chlorides catalyzed by an air- and moisture-stable palladacyclic complex containing P(t-Bu)Cy2 as ligand. The combination of this Pd-catalyzed arylation and base-induced cleavage of the acyl-aryl C-C bond within the α-aryl-α,α- difluoroketone constitutes a one-pot, two-step procedure to synthesize difluoromethylarenes from aryl halides. A broad range of electronically varied aryl and heteroaryl bromides and chlorides underwent these two transformations, providing α-aryl-α,α-difluoroketones, difluoromethylarenes, and difluoromethylheteroarenes in high yields.
METAL-CATALYZED COUPLING OF ARYL AND VINYL HALIDES WITH ALPHA, ALPHA-DIFLUOROCARBONYL COMPOUNDS
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Paragraph 00112; 00140, (2014/10/18)
The coupling of aryl, heteroaryl, and vinyl halides with α,α-difluoroketones or silyl ethers or siylenol ethers of α,α-difluoroketones and α,α-difluoroamides and esters are described. Further derivatization of the coupling products (such as ketone cleavage and Baeyer-Villiger oxidation) is also described.
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.
