89-71-4Relevant articles and documents
Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
K?nig, Burkhard,Wang, Hua,Wang, Shun
supporting information, p. 1653 - 1665 (2021/06/17)
Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.
Light-induced carboxylation of aryl derivatives with cooperative COF as an active photocatalyst and Ni(ii) co-catalyst
Chakrabortty, Pekham,Das, Anjan,Chowdhury, Arpita Hazra,Ghosh, Swarbhanu,Khan, Aslam,Islam, Sk. Manirul
, p. 4738 - 4745 (2021/03/22)
The photocatalytic carboxylation of aryl derivatives was demonstrated under CO2at atmospheric pressure using a mesoporous covalent organic framework (COF) as the active photocatalyst with triethylamine (TEA) as a sacrificial electron source under visible light. A yield of greater than 91% of the isolated product was achieved with 5 mg of catalyst. The reaction cycle is dependent on the use of the Ni(dmg)2co-catalyst and the sacrificial electron donor (TEA). The reaction does not occur in the absence of light (445 nm) even at elevated reaction temperature. We have also demonstrated that a yield of 32% of the isolated product could be obtained with the use of sunlight in the catalytic cycle. Additionally, this heterogeneous catalytic system was recyclable and reusable for several cycles.
Cobalt single atoms anchored on nitrogen-doped porous carbon as an efficient catalyst for oxidation of silanes
Yang, Fan,Liu, Zhihui,Liu, Xiaodong,Feng, Andong,Zhang, Bing,Yang, Wang,Li, Yongfeng
supporting information, p. 1026 - 1035 (2021/02/09)
The oxidation reactions of organic compounds are important transformations for the fine and bulk chemical industry. However, they usually involve the use of noble metal catalysts and suffer from toxic or environmental issues. Here, an efficient, environmentally friendly, and atomically dispersed Co catalyst (Co-N-C) was preparedviaa simple, porous MgO template and etching method using 1,10-phenanthroline as C and N sources, and CoCl2·6H2O as the metal source. The obtained Co-N-C catalyst exhibits excellent catalytic performance for the oxidation of silanes with 97% isolated yield of organosilanol under mild conditions (room temperature, H2O as an oxidant, 1.8 h), and good stability with 95% isolated yield after nine consecutive reactions. The turnover frequency (TOF) is as high as 381 h?1, exceeding those of most non-noble metal catalysts and some noble metal catalysts. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), extended X-ray absorption fine structure (EXAFS), and wavelet transform (WT) spectroscopy corroborate the existence of atomically dispersed Co. The coordination numbers of Co affected by the pyrolysis temperature in Co-N-C-700, Co-N-C-800, and Co-N-C-900 are 4.1, 3.6, and 2.2, respectively. Owing to a higher Co-N3content, Co-N-C-800 shows more outstanding catalytic performance than Co-N-C-700 and Co-N-C-800. Moreover, density functional theory (DFT) calculations reveal that the Co-N3structure exhibits more activity compared with Co-N4and Co-N2, which is because the Co atom in Co-N3was bound with both H atom and Si atom, and it induced the longest Si-H bond.
GPR52 Antagonist Reduces Huntingtin Levels and Ameliorates Huntington's Disease-Related Phenotypes
Wang, Congcong,Zhang, Yu-Fang,Guo, Shimeng,Zhao, Quan,Zeng, Yanping,Xie, Zhicheng,Xie, Xin,Lu, Boxun,Hu, Youhong
, p. 941 - 957 (2020/11/30)
GPR52 is an orphan G protein-coupled receptor (GPCR) that has been recently implicated as a potential drug target of Huntington's disease (HD), an incurable monogenic neurodegenerative disorder. In this research, we found that striatal knockdown of GPR52 reduces mHTT levels in adult HdhQ140 mice, validating GPR52 as an HD target. In addition, we discovered a highly potent and specific GPR52 antagonist Comp-43 with an IC50 value of 0.63 μM by a structure-activity relationship (SAR) study. Further studies showed that Comp-43 reduces mHTT levels by targeting GPR52 and promotes survival of mouse primary striatal neurons. Moreover, in vivo study showed that Comp-43 not only reduces mHTT levels but also rescues HD-related phenotypes in HdhQ140 mice. Taken together, our study confirms that inhibition of GPR52 is a promising strategy for HD therapy, and the GPR52 antagonist Comp-43 might serve as a lead compound for further investigation.
Development of phenyltriazole thiol-based derivatives as highly potent inhibitors of DCN1-UBC12 interaction
Zhou, Wenjuan,Xu, Chenhao,Dong, Guanjun,Qiao, Hui,Yang, Jing,Liu, Hongmin,Ding, Lina,Sun, Kai,Zhao, Wen
, (2021/03/24)
Defective in cullin neddylation 1(DCN1) is a co-E3 ligase that is important for cullin neddylation. Dysregulation of DCN1 highly correlates with the development of various cancers. Herein, from the initial high-throughput screening, a novel hit compound 5a containing a phenyltriazole thiol core (IC50 value of 0.95 μM for DCN1-UBC12 interaction) was discovered. Further structure-based optimization leads to the development of SK-464 (IC50 value of 26 nM). We found that SK-464 not only directly bound to DCN1 in vitro, but also engaged cellular DCN1, suppressed the neddylation of cullin3, and hindered the migration and invasion of two DCN1-overexpressed squamous carcinoma cell lines (KYSE70 and H2170). These findings indicate that SK-464 may be a novel lead compound targeting DCN1-UBC12 interaction.
Ruthenium-Catalyzed Three-Component Alkylation: A Tandem Approach to the Synthesis of Nonsymmetric N,N-Dialkyl Acyl Hydrazides with Alcohols
Bettoni, Léo,Joly, Nicolas,Lohier, Jean-Fran?ois,Gaillard, Sylvain,Poater, Albert,Renaud, Jean-Luc
supporting information, p. 4009 - 4017 (2021/07/02)
The borrowing hydrogen strategy has been applied in the synthesis of nonsymmetric N,N-dialkylated acyl hydrazides via a tandem three-component reaction catalyzed by a phosphine free diaminocyclopentadienone ruthenium tricarbonyl complex. This strategy represents the first direct one-pot approach to nonsymmetric functionalized acyl hydrazides. Different aromatic acyl hydrazides underwent dialkylation with a variety of primary or secondary alcohols and methanol or ethanol as alkylating agents in mild reaction conditions and good yields. Deuterium labelling experiments suggested that the primary or secondary alcohol was the hydrogen source in this tandem process. DFT calculations show that the combination of the tandem mixed product cannot be perfectly explained neither structurally nor electronically, but might be dependent of the physical state of the aldehyde or ketone intermediate (gaz vs. liquid) at the reaction temperature. (Figure presented.).
Copper-promoted direct amidation of isoindolinone scaffolds by sodium persulfate
Lai, Huifang,Lin, Jin,Xu, Jiexin,Zha, Daijun
supporting information, p. 7621 - 7626 (2021/09/22)
Isoindolinones are ubiquitous structural motifs in natural products and pharmaceuticals. Establishing an efficient method for structural modification of isoindolinones could significantly facilitate new drug development. Herein, we describe copper-promoted direct amidation of isoindolinone scaffolds mediated by sodium persulfate. The method exhibits mild reaction conditions and high site-selectivity, and enables the structural modification of the drug indobufen ester with various amides with yields of 49 to 98%. It is also gram-scalable. Additionally, the reaction mechanism appears to involve a radical and a carbocationic pathway.
Hydroxyl radical-mediated oxidative cleavage of CC bonds and further esterification reaction by heterogeneous semiconductor photocatalysis
Hong, Mei,Jia, Rui,Miao, Hongyan,Ni, Bangqing,Niu, Tengfei,Wang, Hui
, p. 6591 - 6597 (2021/09/10)
A hydroxyl radical-mediated aerobic cleavage of alkenes and further sequence esterification reaction for the preparation of carbonyl compounds have been developed by using tubular carbon nitride (TCN) as a general heterogeneous photocatalyst under an oxygen atmosphere with visible light irradiation. This protocol has an excellent substrate scope and gives the desired aldehydes, ketones and esters in moderate to high yields. Importantly, this metal-free procedure employed photogenerated hydroxyl radicals in situ as green oxidation active species, avoiding the present additional initiators. The reaction could be carried out under solar light irradiation and was applicable to large-scale reactions. Furthermore, the recyclable TCN catalyst could be used several times without a significant loss of activities.
Method for preparing carboxylic ester compounds by oxidizing and breaking carbon-carbon bonds of secondary alcohol compounds
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Paragraph 0040-0041; 0092, (2021/06/02)
The invention discloses a method for preparing carboxylic ester compounds by oxidizing and breaking carbon-carbon bonds of secondary alcohol compounds. The method comprises the following steps: adding a secondary alcohol compound, an additive and a nitrogen-doped mesoporous carbon loaded monatomic catalyst into a fatty primary alcohol solvent, putting into a pressure container, sealing, introducing oxygen source gas with a certain pressure, controlling the pressure of the oxygen source gas to be 0.1-1 MPa and the reaction temperature to be 80-150 DEG C, and obtaining a product after the reaction to be the carboxylic ester compound. The nitrogen-doped mesoporous carbon-loaded monatomic catalyst adopted by the invention is high in activity, the highest separation yield of the carboxylic ester compound as a reaction product reaches 99%, the method is wide in application range, the reaction conditions are easy to control, the catalyst can be recycled, the post-treatment is simple, and the method is suitable for industrial production.
Mild Copper-Catalyzed Addition of Arylboronic Esters to Di- tert -butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates
Xu, Jin-Di,Su, Xiao-Bo,Wang, Cai,Yao, Li-Wei,Liu, Jing-Hui,Hu, Guo-Qin
supporting information, p. 833 - 837 (2021/02/26)
An efficient copper-catalyzed addition of arylboronic esters to (Boc) 2O was developed. The reaction can be conducted under exceedingly mild conditions and is compatible with a variety of synthetically relevant functional groups. It therefore represents a useful alternative route for the synthesis of methyl arylcarboxylates. A preliminary mechanistic study indicated the involvement of an addition-elimination mechanism.
