715-80-0Relevant academic research and scientific papers
Palladium-catalyzed fluoroacylation of (Hetero)arylboronic acid with fluorothioacetates at ambient temperature
Ban, Shu-Rong,Cao, Ya-Fang,Dai, Hui-Xiong,Wang, Xing,Xu, Hui,Yi, Xing
supporting information, (2020/03/23)
A palladium-catalyzed fluoroacylation of (hetero)aryl boronic acid with the fluorothioacetates is described at ambient temperature. A variety of aryl, and heteroaryl boronic acids are compatible in the reaction, affording the corresponding fluoroalkyl ketones in moderate to good yields. Further late-stage di-, and trifluoroacylation of drug molecule clofibrate and estrone demonstrated the synthetic practicability of this protocol.2009 Elsevier Ltd. All rights reserved.
Controllable catalytic difluorocarbene transfer enables access to diversified fluoroalkylated arenes
Fu, Xia-Ping,Xue, Xiao-Song,Zhang, Xue-Ying,Xiao, Yu-Lan,Zhang, Shu,Guo, Yin-Long,Leng, Xuebing,Houk, Kendall N.,Zhang, Xingang
, p. 948 - 956 (2019/11/05)
Difluorocarbene has important applications in pharmaceuticals, agrochemicals and materials, but all these applications proceed using just a few types of reaction by taking advantage of its intrinsic electrophilicity. Here, we report a palladium-catalysed strategy that confers the formed palladium difluorocarbene (Pd=CF2) species with both nucleophilicity and electrophilicity by switching the valence state of the palladium centre (Pd(0) and Pd(ii), respectively). Controllable catalytic difluorocarbene transfer occurs between readily available arylboronic acids and the difluorocarbene precursor diethyl bromodifluoromethylphosphonate (BrCF2PO(OEt)2). From just this simple fluorine source, difluorocarbene transfer enables access to four types of product: difluoromethylated and tetrafluoroethylated arenes and their corresponding fluoroalkylated ketones. The transfer can also be applied to the modification of pharmaceuticals and agrochemicals as well as the one-pot diversified synthesis of fluorinated compounds. Mechanistic and computational studies consistently reveal that competition between nucleophilic and electrophilic palladium difluorocarbene ([Pd]=CF2) is the key factor controlling the catalytic difluorocarbene transfer.
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
Difluoromethylation of carboxylic acids via the addition of difluorinated phosphorus ylide to acyl chlorides
Trifonov, Alexey L.,Levin, Vitalij V.,Struchkova, Marina I.,Dilman, Alexander D.
, p. 5304 - 5307 (2017/11/06)
A one-step protocol for the difluoromethylation of carboxylic acids is described. The reaction involves the interaction of intermediate acyl chlorides with in situ generated difluorinated phosphorus ylide Ph3P=CF2. Aromatic acids can be selectively transformed within one step either to bis-difluoromethylated alcohols or to difluorinated ketones depending on the particular reaction conditions. For bulky α-branched carboxylic acids, only ketones are produced.
Practical Access to Difluoromethyl Ketones via Straightforward Decarboxylative Difluorination of β-Ketoacids
Li, Yin-Long,Li, Jian,Deng, Jun
, p. 1407 - 1412 (2017/04/18)
A facile synthetic approach to a series of difluoromethyl ketones from β-ketoacids has been described. This transformation is achieved through the straightforward decarboxylative difluorination of β-ketoacids in the absence of any catalyst. Furthermore, the resulted difluoromethyl ketones can be easily converted into corresponding difluoromethylated building blocks for pharmaceuticals and materials. (Figure presented.).
Preparation of a stable trifluoroborate salt for the synthesis of 1-aryl-2,2-difluoro-enolethers and/or 2,2-difluoro-1-aryl-ketones via palladium-mediated cross-coupling
Katz, Jason D.,Lapointe, Blair T.,Dinsmore, Christopher J.
supporting information; experimental part, p. 8866 - 8869 (2010/03/02)
(Chemical Equation Presented) A bench-stable potassium trifluoroborate enol ether reagent has been prepared. This reagent is suitable for the incorporation of 2,2-difluoroenolethers into aryl and heteroaryl systems via palladium-mediated cross-coupling wi
Microwave assisted fluorination: an improved method for side chain fluorination of substituted 1-arylethanones
Krane Thvedt, Thor H?kon,Fuglseth, Erik,Sundby, Eirik,Hoff, B?rd Helge
experimental part, p. 9550 - 9556 (2010/02/27)
A two-step, one-pot microwave (MW) assisted fluorination of 1-arylethanones to their corresponding 1-aryl-2-fluoroethanones has been developed. The first step utilises Selectfluor as a fluorinating agent in methanol forming 1-aryl-2-fluoroethanones and their corresponding dimethyl acetals. In the second step, water is added and Selectfluor acts as a Lewis acid in the hydrolytic cleavage of the dimethyl acetals. Compared to the thermal synthesis, the MW assisted method leads to a reduction in reaction time both in the fluorination and for the dimethyl acetal cleavage. Moreover, the one-pot procedure reduces reagent and solvent consumption. The method is best suited for the preparation of 1-aryl-2-fluoroethanones containing substituents that deactivates electrophilic aromatic substitution, however highly electron deficient ketones such as 1-(3,5-dinitrophenyl)ethanone reacts more slowly. Reactions using electron rich aromatic ketones had a low regioselectivity, and also produced fluoroaromatic products.
Facile preparation of di- and monofluoromethyl ketones from trifluoromethyl ketones via fluorinated enol silyl ethers
Surya Prakash,Hu,Olah
, p. 357 - 362 (2007/10/03)
Di- and monofluoromethyl ketones were prepared from the readily available trifluoromethyl ketones in high yields. Magnesium metal mediated reductive defluorination readily generates fluorinated enol silyl ethers, which upon fluoride or acid assisted hydrolysis give the respective ketones in good to excellent yields.
