437552-71-1Relevant academic research and scientific papers
A Carbene Strategy for Progressive (Deutero)Hydrodefluorination of Fluoroalkyl Ketones
Bi, Xihe,Sivaguru, Paramasivam,Song, Qingmin,Wang, Zikun,Zanoni, Giuseppe,Zhang, Xiaolong,Zhang, Xinyu
, (2021/12/23)
Hydrodefluorination is one of the most promising chemical strategies to degrade perfluorochemicals into partially fluorinated compounds. However, controlled progressive hydrodefluorination remains a significant challenge, owing to the decrease in the stre
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.
Direct and Chemoselective Synthesis of Tertiary Difluoroketones via Weinreb Amide Homologation with a CHF2-Carbene Equivalent
Miele, Margherita,Citarella, Andrea,Micale, Nicola,Holzer, Wolfgang,Pace, Vittorio
supporting information, p. 8261 - 8265 (2019/10/16)
The homologation of Weinreb amides into difluoromethylketones with a formal nucleophilic CHF2 transfer agent is reported. Activating TMSCHF2 with potassium tert-amylate enables a convenient access to the difluorinated homologation re
Conversion of methyl ketones and methyl sulfones into α-deutero-α,α-difluoromethyl ketones and α-deutero-α,α-difluoromethyl sulfones in three synthetic steps
Sowaileh, Munia F.,Han, Changho,Hazlitt, Robert A.,Kim, Eun Hoo,John, Jinu P.,Colby, David A.
supporting information, p. 396 - 400 (2017/01/10)
Deuterodifluoromethyl ketones and sulfones were assembled in three synthetic steps from methyl ketones and sulfones, respectively. The key synthetic transformation is the deuteration of the difluorocarbanion generated by the release of trifluoroacetate from highly α-fluorinated gem-diols. High levels of deuterium on the “CF2D” group were routinely observed. This strategy is mild and versatile and it can be applied to both ketones and sulfones without additional concerns of over- or under-fluorination. Additional examples address issues of over-deuteration when compounds with other acidic protons are subjected to the reaction conditions. This process not only demonstrates a new method to install a “CF2D” group but also extends the scope of trifluoroacetate release to sulfones.
