79-03-8Relevant articles and documents
Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses
Liang, Fengying,Eda, Kazuo,Okazoe, Takashi,Wada, Akihiro,Mori, Nobuaki,Konishi, Katsuhiko,Tsuda, Akihiko
, p. 6504 - 6517 (2021/05/06)
The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.
Rhodium(III)-catalyzed chemodivergent annulations between phenyloxazoles and diazos via C–H activation
Zhang, Xueguo,Wang, Peigen,Zhu, Liangwei,Chen, Baohua
supporting information, p. 695 - 699 (2020/06/28)
Acid-controlled, chemodivergent and redox-neutral annulations for the synthesis of isocoumarins and isoquinolinones have been realized via Rh(III)-catalyzed C[sbnd]H activation. Diazo compounds act as a carbene precursor, and coupling occurs in one-pot process, where adipic acid and trimethylacetic acid promote chemodivergent cyclizations.
Synthesis, experimental and theoretical study of novel 2-haloalkyl (-CF2H, -CCl2H, -CF2CF3)-, 3-bromo and bromomethyl substituted chromones
Narváez O, Ena G.,Bonilla V., Pablo M.,Zurita, Daniel A.,Alcívar L., Christian D.,Heredia-Moya, Jorge,Ulic, Sonia E.,Jios, Jorge L.,Piro, Oscar E.,Echeverría, Gustavo A.,Langer, Peter
, (2021/01/12)
A set of seven new chromones with 2-haloalkyl (-CF2H, -CCl2H, -CF2CF3) and 3-bromo and bromomethyl substituents were synthesized. The novel compounds were studied by DFT calculations and characterized by vibrational spectroscopy (IR and Raman) in solid state, and NMR (1H, 13C and 19F) and UV–vis spectroscopy in solution. The crystal structure of 3-dibromomethyl-2-difluoromethyl chromone was determined by X-ray diffraction. Due to extended π-bond delocalization, the organic framework is planar and lies on a crystallographic m-mirror plane. The intermolecular non-covalent interactions of 3-dibromomethyl-2-difluoromethyl chromone, as π?π stacking arrangements, F?H hydrogen bonds and O?Br contacts were evaluated by Hirshfeld surfaces analysis. These intermolecular contacts, which affect the absorption bands location of the involved groups, were also detected in the vibrational spectra.
Electrodimerization ofN-Alkoxyamides for the Synthesis of Hydrazines
Nasier, Abudulajiang,Chang, Xihao,Guo, Chang
, p. 16068 - 16076 (2021/09/18)
An efficient and valuable N-N dimerization reaction ofN-alkoxyamides is reported under undivided electrolytic conditions. This electrochemical strategy provides a powerful way to access a wide range of advanced, highly functionalized hydrazines. Remarkably, anN-centered radical generated from the cleavage of the N-H bond under electrolytic conditions plays a crucial role in this transformation. Furthermore, variousN-alkoxyamides bearing different substituents are suitable in this transformation, furnishing the corresponding hydrazines in up to 92% yield.
Neutrophil-Selective Fluorescent Probe Development through Metabolism-Oriented Live-Cell Distinction
Gao, Min,Lee, Sun Hyeok,Park, Sang Hyuk,Ciaramicoli, Larissa Miasiro,Kwon, Haw-Young,Cho, Heewon,Jeong, Joseph,Chang, Young-Tae
supporting information, p. 23743 - 23749 (2021/10/14)
Human neutrophils are the most abundant leukocytes and have been considered as the first line of defence in the innate immune system. Selective imaging of live neutrophils will facilitate the in situ study of neutrophils in infection or inflammation events as well as clinical diagnosis. However, small-molecule-based probes for the discrimination of live neutrophils among different granulocytes in human blood have yet to be reported. Herein, we report the first fluorescent probe NeutropG for the specific distinction and imaging of active neutrophils. The selective staining mechanism of NeutropG is elucidated as metabolism-oriented live-cell distinction (MOLD) through lipid droplet biogenesis with the help of ACSL and DGAT. Finally, NeutropG is applied to accurately quantify neutrophil levels in fresh blood samples by showing a high correlation with the current clinical method.
Synthesis of N-trifluoromethyl amides from carboxylic acids
Flavell, Robert R.,Liu, Jianbo,Parker, Matthew F. L.,Toste, F. Dean,Wang, Sinan,Wilson, David M.
supporting information, p. 2245 - 2255 (2021/08/12)
Found in biomolecules, pharmaceuticals, and agrochemicals, amide-containing molecules are ubiquitous in nature, and their derivatization represents a significant methodological goal in fluorine chemistry. Trifluoromethyl amides have emerged as important functional groups frequently found in pharmaceutical compounds. To date, there is no strategy for synthesizing N-trifluoromethyl amides from abundant organic carboxylic acid derivatives, which are ideal starting materials in amide synthesis. Here, we report the synthesis of N-trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature. Through this strategy, isothiocyanates are desulfurized with AgF, and then the formed derivative is acylated to afford N-trifluoromethyl amides, including previously inaccessible structures. This method shows broad scope, provides a platform for rapidly generating N-trifluoromethyl amides by virtue of the diversity and availability of both reaction partners, and should find application in the modification of advanced intermediates.
Palladium-Catalyzed 2-(Neopentylsulfinyl)aniline Directed C–H Acetoxylation and Alkenylation of Arylacetamides
Barysevich, Maryia V.,Laktsevich-Iskryk, Marharyta V.,Krech, Anastasiya V.,Zhabinskii, Vladimir N.,Khripach, Vladimir A.,Hurski, Alaksiej L.
supporting information, p. 937 - 943 (2020/02/25)
The 2-(neopentylsulfinyl)aniline directing group that promotes rapid palladium-catalyzed C–H acetoxylation and alkenylation of arylacetamides has been developed. The acetoxylation reaches completion within only 40 min at 100 °C and leads to the bis-functionalized products. Alternatively, the reaction can be carried out at room temperature, which is beneficial for sensitive substrates. For the alkenylation, we have developed a protocol in which easily available 1-substituted cyclopropanols were employed as equivalents of vinyl ketones.
Visible-Light-Assisted Gold-Catalyzed Fluoroarylation of Allenoates
Feng, Chao,Tang, Hai-Jun,Zhang, Xinggui,Zhang, Yu-Feng
supporting information, p. 5242 - 5247 (2020/02/28)
A strategically novel synthetic method for the fluoroarylation of allenic ester was developed that enables the expedient construction of a host of β-fluoroalkyl-containing cinnamate derivatives. The reaction proceeds through visible-light-promoted gold redox catalysis, occurs smoothly under very mild reaction conditions, accommodates a large variety of functional groups, and more importantly allows the incorporation of fluorine and aryl groups with excellent regio- and stereoselectivity. The concomitant activation mode for both the allene motif and the hydrogen fluoride is key for the success of the reaction.
Isoalantolactone derivative, pharmaceutical composition and application thereof
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Paragraph 0014, (2019/02/02)
The invention relates to an isoalantolactone derivative, a pharmaceutical composition and application thereof, especially use of the isoalantolactone derivative shown as formula (I) or a salt pharmaceutical compound thereof in preparation of adjuvant drugs treating cancer, a pharmaceutical composition containing a therapeutically effective amount of isoalantolactone derivative (I) or its salt anda pharmaceutically acceptable carrier or a composition with other anticancer drugs.
Pd/Cu-Catalyzed Cascade C(sp3)-H Arylation and Intramolecular C-N Coupling: A One-Pot Synthesis of 3,4-2 H-Quinolinone Skeletons
Xiao, Han-Zhi,Wang, Wen-Shu,Sun, Yu-Song,Luo, Hao,Li, Bo-Wen,Wang, Xiao-Dong,Lin, Wei-Li,Luo, Fei-Xian
supporting information, p. 1668 - 1671 (2019/03/11)
In this letter, we successfully explored a cascade Pd/Cu-catalyzed intermolecular C(sp3)-H arylation of amides and intramolecular C-N coupling reaction. This method provides a one-pot strategy to synthesize 3,4-2H-quinolinone with good regioselectivity of C-H arylation and C-N coupling from C-I and C-X bonds from readily available starting materials.
