- Synthesis of Unsymmetrical 1,4-Dicarbonyl Compounds by Photocatalytic Oxidative Radical Additions
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Herein we report a photocatalytic oxidative radical addition reaction for the synthesis of unsymmetrical 1,4-dicarbonyl compounds. This reaction utilizes a desulfurization process to generate electrophilic radicals, which add to α-halogenated alkenes and undergo further oxidation to deliver 1,4-dicarbonyl compounds. This mild and highly efficient method provides a valuable alternative to known strategies.
- Dong, Ya,Li, Ruining,Zhou, Junliang,Sun, Zhankui
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p. 6387 - 6390
(2021/08/23)
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- COMPOUND HAVING BET INHIBITORY ACTIVITY AND PREPARATION METHOD AND USE THEREFOR
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The invention relates to the field of pharmaceutical chemistry. Specifically, the present invention relates to a series of BET (bromodomain and extra-terminal domain) inhibitors having a novel structure, particularly inhibitors targeting BRD4 (Bromodomain-containing protein 4), and a preparation method and use therefor. The structure thereof is shown in the following general formula (I). Said compounds or a stereoisomer, racemate, geometric isomer, tautomer, prodrug, hydrate, solvate, or crystal form thereof, or a pharmaceutically acceptable salt thereof, and the pharmaceutical compsosition thereof can be used for the treatment and/or prevention of related diseases mediated by bromodomain proteins.
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Paragraph 0157-0159
(2020/12/22)
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- 1-butyl-3-methylimidazolium bromide as a solvent and precatalyst for stetter reaction
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Stetter reaction between aromatic aldehydes and acrylonitrile/ethyl acrylate performing in [Bmim]Br in the presence of NaOH is described. N-Heterocyclic carbene (NHC) generates in situ is shown to be an efficient catalyst. Benzoin condensation also occured as side reaction.
- Phungpis, Baramee,Hahnvajanawong, Viwat
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p. 2028 - 2032
(2020/09/02)
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- Combined Photoredox/Enzymatic C?H Benzylic Hydroxylations
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Chemical transformations that install heteroatoms into C?H bonds are of significant interest because they streamline the construction of value-added small molecules. Direct C?H oxyfunctionalization, or the one step conversion of a C?H bond to a C?O bond, could be a highly enabling transformation due to the prevalence of the resulting enantioenriched alcohols in pharmaceuticals and natural products,. Here we report a single-flask photoredox/enzymatic process for direct C?H hydroxylation that proceeds with broad reactivity, chemoselectivity and enantioselectivity. This unified strategy advances general photoredox and enzymatic catalysis synergy and enables chemoenzymatic processes for powerful and selective oxidative transformations.
- Betori, Rick C.,May, Catherine M.,Scheidt, Karl A.
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supporting information
p. 16490 - 16494
(2019/11/03)
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- Nickel-Catalyzed Transformation of Diazoacetates to Alkyl Radicals Using Alcohol as a Hydrogen Source
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A nickel-catalyzed transformation of diazoacetates to α-carbonyl methylene radicals has been disclosed in the presence of hyperoxide using ethanol as a hydrogen source and solvent. This strategy is successfully applied in the formation of indolin-2-ones or 1,4-dicarbonyl compounds from acrylamides or enamides in moderate to good yields. These reactions undergo radical addition onto C-C double bonds followed by a cyclization/oxidation or an oxidation/hydrolysis process, respectively.
- Zhao, Jingjing,Li, Pan,Xu, Yaohua,Shi, Yixin,Li, Fuwei
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supporting information
p. 9386 - 9390
(2019/11/28)
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- Visible-Light Photocatalytic Preparation of 1,4-Ketoaldehydes and 1,4-Diketones from α-Bromoketones and Alkyl Enol Ethers
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A Ru2+-photocatalyzed, visible-light-mediated ATRA reaction for the straightforward preparation of 1,4-ketoaldehydes, 1,4-diketones, and 1,4-ketoesters, which are of difficult access by other means, is reported herein. This method employs readily accessible α-bromoketones and alkyl vinyl ethers as starting materials, allowing the construction of secondary, tertiary, and challenging quaternary centers. In addition, the synthetic usefulness of this method is illustrated by applying it to the construction of substituted pyrroles.
- García-Santos, William H.,Mateus-Ruiz, Jeferson B.,Cordero-Vargas, Alejandro
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supporting information
p. 4092 - 4096
(2019/06/17)
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- A process for preparing γ - ketone carbonyl compounds
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The present invention discloses a gamma-ketone carbonyl compound preparation method, wherein in the presence of an oxidizing agent, a styrene compound and ethyl diazoacetate are adopted as reactants, copper or a copper compound is adopted as a catalyst, DABCO is adopted as an alkali, and a free radical reaction is performed in a polar solvent isopropyl alcohol to obtain the product gamma-ketone carbonyl compound. According to the method of the present invention, the reaction activity of the catalyst is high, the reaction conditions are mild, the substrate application range is wide, the post-treatment is convenient, the yield of the target product is high, the preparation process is simple, and the sources of the used raw materials are wide.
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Paragraph 0110; 0111; 0112
(2018/07/30)
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- Discovery of Oxime Ethers as Hepatitis B Virus (HBV) Inhibitors by Docking, Screening and In Vitro Investigation
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A series of oxime ethers with C6-C4 fragment was designed and virtually bioactively screened by docking with a target, then provided by a Friedel-Crafts reaction, esterification (or amidation), and oximation from p-substituted phenyl derivatives (Methylbenzene, Methoxybenzene, Chlorobenzene). Anti-hepatitis B virus (HBV) activities of all synthesized compounds were evaluated with HepG2.2.15 cells in vitro. Results showed that most of compounds exhibited low cytotoxicity on HepG2.2.15 cells and significant inhibition on the secretion of HBsAg and HBeAg. Among them, compound 5c-1 showed the most potent activity on inhibiting HBsAg secretion (IC50 = 39.93 μM, SI = 28.51). Results of the bioactive screening showed that stronger the compounds bound to target human leukocyte antigen A protein in docking, the more active they were in anti-HBV activities in vitro.
- Tan, Jie,Zhou, Min,Cui, Xinhua,Wei, Zhuocai,Wei, Wanxing
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- Cu-based carbene involved in a radical process: A new crossover reaction to construct γ-peroxy esters and 1,4-dicarbonyl compounds
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Through merging Cu-based carbenes in a radical process, a novel crossover reaction has been successfully established, leading to the facile and efficient syntheses of various γ-peroxy esters and 1,4-dicarbonyl compounds. Considering that both Cu-based carbene complexes and radicals are extremely reactive, and therefore exist only in extraordinarily low concentrations, the high selectivity of this coupling reaction is unusual.
- Jiang, Jiewen,Liu, Jiajun,Yang, Ling,Shao, Ying,Cheng, Jiang,Bao, Xiaoguang,Wan, Xiaobing
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supporting information
p. 14728 - 14731
(2015/10/05)
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- Fused triazole derivatives as gamma secretase modulators
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The present invention provides fused bicyclic triazole derivatives of Formula (I) useful as gamma secretase modulators (GSM), for the treatment of Alzheimer's disease and related diseases.
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Paragraph 0064
(2014/02/15)
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- FUSED TRIAZOLE DERIVATIVES AS GAMMA SECRETASE MODULATORS
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The present invention provides fused bicyclic triazole derivatives of Formula (I) useful as gamma secretase modulators (GSM), for the treatment of Alzheimer's disease and related diseases.
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Page/Page column 32; 33
(2014/02/15)
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- Benzoin condensation and stetter reaction catalysed by N,N-dimethylbenzimidazolium iodide in [Bmim][OH]
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N,N-Dimethylbenzimidazolium iodide catalysed benzoin condensation and Stetter reaction in 1-butyl-3-methylimidazolium hydroxide [bmim][OH] which acts as a basic catalyst as well as a solvent for the reactions are described. The recycled reaction media containing benzimidazolium salt can be reused for several times without significant loss of efficiency.
- Phungpis, Baramee,Hahnvajanawong, Viwat,Theramongkol, Parinya
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p. 933 - 939
(2015/02/19)
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- Synthesis of γ-, δ-, and ε-lactams by asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)iminoesters
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Highly enantiomerically enriched γ- and δ-lactams have been prepared by a simple and very efficient procedure that involves the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)iminoesters followed by desulfinylation of the nitrogen atom and spo
- Guijarro, David,Pablo, Oscar,Yus, Miguel
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p. 3647 - 3654
(2013/05/22)
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- Tris(4-methoxylphenyl)phosphine-catalyzed C-C bond formation reaction: Mutual addition of aromatic aldehydes and ethyl acrylate
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A highly efficient intermolecular mutual addition of aromatic aldehydes with ethyl acrylate was developed by using tris(4-methoxylphenyl)phosphine as the catalyst. The reaction corresponds to the construction of 1,4-dicarbonyl compound and allylic alcohol
- Teng, Jun-Jiang,Qiao, Yan-Hui,Zhang, Qing,Li, Chun-Hai,Huang, Min
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p. 848 - 858
(2013/02/25)
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- Efficient synthesis of γ-keto esters from enamines and EDA
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The reaction of enamines with ethyl diazoacetate (EDA) catalyzed by dirhodium and copper complexes provided γ-keto esters in good yields. The influences of catalyst, reaction solvent, temperature, and structure of enamines on this transformation were inve
- Huang, Dan,Yan, Ming,Zhao, Wei-Jie,Shen, Qi
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p. 745 - 750
(2007/10/03)
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- Carbon-carbon bond cleavage of α-substituted benzoins by retro-benzoin condensation; A new method of synthesizing ketones
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When α-benzylbenzoin (3a, α-benzyl-α-hydroxybenzyl phenyl ketone) was treated with potassium cyanide (1) in N,N-dimethylformamide at 80°C for 1h, the carbon-carbon bond was cleaved, resulting in the formation of deoxybenzoin (4a, benzyl phenyl ketone) and benzaldehyde (2a). This carbon- carbon bond cleavage proceeds through a retro-benzoin condensation mechanism. This method of synthesizing ketones was applied to several α-substituted benzoins (3), and the corresponding ketones (4) were formed in good yields. Further, we found that the cyanide ion-donating ability of tetrabutylammonium cyanide (6, Bu4NCN) is more effective than that of potassium cyanide (1, KCN). As expected from the chemical analogy between cyanide ion and azolium ylide, several azolium salts (7) can also be employed in the retro-benzoin condensation as catalysts. The benzoin derivatives 3 were synthesized in the following three ways; reaction of alkyl halide (9) with benzoin (5), Michael addition of benzoin (5) with acceptors (10), and Grignard reaction of benzils (8). Alkylation of the benzoins without isolation, followed by carbon-carbon bond cleavage, readily afforded the corresponding ketones (4).
- Miyashita, Akira,Suzuki, Yumiko,Okumura, Yoko,Iwamoto, Ken-Ichi,Higashino, Takeo
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- ortho-halogeno substituents effect in asymmetric cyclization of 4-aryl-4-pentenals using a rhodium catalyst
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Asymmetric cyclization of 4-aryl-4-pentenals by using a cationic [Rh((R)-BINAP)]ClO4 afforded (3R)-3-substituted cyclopentanones; on the other hand, the cyclization of 4-pentenals bearing ortho-halogeno phenyl groups afforded the opposite (3S)-ones.
- Fujio, Masakazu,Tanaka, Masakazu,Wu, Xiao-Ming,Funakoshi, Kazuhisa,Sakai, Kiyoshi,Suemune, Hiroshi
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p. 881 - 882
(2007/10/03)
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- Synthesis of ketones by retro-benzoin condensation catalyzed by potassium cyanide
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The treatment of 2-benzyl-1,2-diphenyl-2-hydroxyethanone (3a, benzylbenzoin) with potassium cyanide in DMF gave deoxybenzoin (4a). The formation of deoxybenzoin (4a) proceeds through retro-benzoin condensation by catalytic action of cyanide ion. Similarly, retro-benzoin condensation applied to several substituted benzoins 3 resulted in the formation of the corresponding ketones 4 in excellent yields.
- Miyashita,Suzuki,Okumura,Higashino
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p. 252 - 254
(2007/10/03)
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- Synthesis of 1,4-Keto Esters and 1,4-Diketones via Palladium-Catalyzed Acylation of Siloxycyclopropanes. Synthetic and Mechanistic Studies
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The reaction of a variety of siloxycyclopropanes with acid chlorides in the presence of a catalytic amount of a palladium/phosphine complex gives 1,4-dicarbonyl compounds to good yield. 1-Alkoxy-1-(trialkylsiloxy)-cyclopropanes react with both aromatic and aliphatic acid chlorides in chloroform to give 1,4-keto esters.Synthesis of 1,4-diketones by the acylation of 1-alkyl- or 1-aryl-1-siloxycyclopropanes has been achieved by carrying out the reaction if HMPA under 10-20 atm of carbon monoxide.Kinetic studies and product analysis revealed the unique mechanism of this reaction, which involves rate-determining cleavage of the strained cyclopropane carbon-carbon bond with a coordinatively unsaturated acylpalladium chloride complex.Ab initio calculations of hydroxylated cyclopropane model compounds showed that the unique reactivities of the siloxycyclopropanes may be correlated with the molecular orbital properties of these compounds rather than their ground-state structural properties.
- Fujimura, Tsutomu,Aoki, Satoshi,Nakamura, Eiichi
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p. 2809 - 2821
(2007/10/02)
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- Palladium- and platinum-catalyzed reaction of siloxycyclopropanes with acid chlorides. A homoenolate route to 1,4-dicarbonyl compounds
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1,4-Keto esters and 1,4-diketones have been synthesized by the palladium-catalyzed reaction of siloxycylopropanes and acid chlorides.
- Aoki,Fujimura,Nakamura,Kuwajima
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p. 6541 - 6544
(2007/10/02)
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- Generation of 2-Carboethoxyethylzinc Iodide and 3-Carboethoxypropylzinc Iodide and Their Application to the Synthesis of γ- and δ-Keto Esters
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2-Carboethoxyethylzinc iodide and 3-carboethoxypropylzinc iodide are generated by the reaction of the corresponding iodoesters with Zn-Cu couple and utilized for the palladium catalyzed coupling reaction with acid chloride to quantitatively provide gamma- and delta- keto esters, respectively
- Tamaru, Yoshinao,Ochiai, Hirofumi,Nakamura, Tatsuya,Tsubaki, Kazunori,Yoshida, Zen-ichi
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p. 5559 - 5562
(2007/10/02)
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- THE REACTION OF O-ETHYL SUCCINIMIDE WITH ARYLLITHIUM COMPOUNDS: AN EFFICIENT METHOD FOR THE INTRODUCTION OF 3-ETHOXYCARBONYLPROPIONYL GROUP TO AROMATIC COMPOUNDS
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O-Ethyl succinimide (I) was found to be an efficient reagent for the introduction of 3-ethoxycarbonylpropionyl group (-COCH2CH2COOEt) to aromatic compounds by a single operation under mild conditions.
- Nagasaka, Tatsuo,Hamaguchi, Fumiko,Ozawa, Naganori,Kosugi, Yoshiyuki,Ohki, Sadao
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p. 291 - 293
(2007/10/02)
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