1123-27-9Relevant academic research and scientific papers
Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: From C-C bond cleavage to C-C bond ligation
Loschonsky, Sabrina,Wacker, Tobias,Waltzer, Simon,Giovannini, Pier Paolo,McLeish, Michael J.,Andrade, Susana L. A.,Müller, Michael
, p. 14402 - 14406 (2014)
ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94% enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant.
Catalytic osmylation of allenic compounds. Synthesis of α-hydroxyketo amino acid precursors
David, Katerine,Ariente, Cecile,Greiner, Alfred,Gore, Jacques,Cazes, Bernard
, p. 3335 - 3338 (1996)
Osmium tetroxyde-catalyzed dihydroxylation of allenic compounds in the presence of N-Methylmorpholine Oxide leads to α-ketols. Regioselectivity of this oxidation procedure with allenic α-amino acid precursors is greatly influenced by the nature and the remoteness of the protected amino acid group.
Efficient oxidation of 1,2-diols into a-hydroxyketones catalyzed by organotin compounds
Maki, Toshihide,Iikawa, Shinya,Mogami, Gen,Harasawa, Hitomi,Matsumura, Yoshihiro,Onomura, Osamu
, p. 5364 - 5370 (2009)
Electrochemical oxidation of 1,2-diols with a catalytic amount of an organotin compound and a bromide ion as mediators has been developed. Various cyclic and acyclic 1,2-diols were oxidized into the corresponding α-hydroxyketones in good to excellent yields without C-C bond cleavage. Also, oxidation with the use of chemical oxidants was accomplished in the presence of a catalytic amount of an organotin compound. These reactions could discriminate 1,2-diols from isolated hydoxyl groups or 1,3-diols. In the case of a conformationally restricted cyclic 1,2-diol, the axial hydroxyl group was oxidized exclusively. Mono-, di-, and trialkylated tin compounds were examined as mediators and dialkylated tin compounds showed higher catalytic activity than mono- and trisubstituted ones. Me2SnCl2 was found to be the most suitable mediator for the selective oxidation..
Synthesis and Fungicidal Activity of (E)-5-[1-(2-Oxo-1-oxaspiro[4,5]dec/non-3-en-3-yl)ethylidene]-2-aminoimidazolin-4-one Derivatives
Tang, Bo,Guan, Aiying,Zhao, Yu,Jiang, Jiazhen,Wang, Mingan,Zhou, Ligang
, p. 1133 - 1140 (2017)
The novel fungicidal agents, (E)-5-[1-(2-oxo-1-oxaspiro[4,5]dec/non-3-en-3-yl)ethylidene]-2-aminoimidazolin- 4-one derivatives, were designed and synthesized in moderate to excellent yields in four steps using α-hydroxyketone and diketene as raw materials and characterized by HR-ESI-MS, 1H NMR and X-ray diffraction. The preliminary bioassay showed that some of these compounds, such as 5e, 6a, 6e, and 7 h exhibit 87.8%, 91.3%, 89.9% and 87.8% inhibition rates against Sclerotinia scleotiorum, 3b, 3c, 4c and 7 h exhibit 96.4%, 92.5%, 90.3% and 76.9% inhibition rates against Phytophthora capsici at the concentration of 50 μg/mL, respectively. These compounds exhibited significant fungicidal activities against S. scleotiorum and P. capsici with EC50 values of 2.56–11.60 μg/mL, and compounds 6e and 7 h exhibited weak inhibition against the spore germination of S. scleotiorum, while the spore germination of P. capsici was strongly inhibited by compound 7 h solution. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observation indicated that compound 7 h had a significant impact on the structure and function of the hyphal cell wall of P. capsici mycelium.
A green and recyclable CuSO4·5H2O/ionic liquid catalytic system for the CO2-promoted hydration of propargyl alcohols: an efficient assembly of α-hydroxy ketones
Chen, Cheng,Chen, Yiyun,Hu, Jia,Huang, Leilei,Verpoort, Francis,Wang, Yu,Yuan, Ye,Zhao, Yufeng,Zheng, Jiayun
, (2021/12/03)
α-Hydroxy ketones are important building blocks in biological, pharmaceutical and synthetic chemistry. In this work, diverse α-hydroxy ketones were efficiently constructed through the CO2-promoted hydration process of propargyl alcohols, which was catalyzed by a system consisted of economical CuSO4·5H2O and a green 1-butyl-3-methylimidazolium acetate ionic liquid. Particularly, this catalytic system exhibited excellent activity under atmospheric CO2 or even mimetic flue gas (20 vol% of CO2). Moreover, this system employed the lowest metal loading ever reported (0.004–0.25 mol%) meanwhile reached the highest turnover number (11700) for the target hydration reaction. Additionally, this is the first reported Cu catalytic system with reliable recyclability, which could be easily reused at least 6 times with yields higher than 85%.
A CO2-mediated base catalysis approach for the hydration of triple bonds in ionic liquids
Han, Buxing,Ke, Zhengang,Li, Ruipeng,Liu, Zhimin,Tang, Minhao,Wang, Yuepeng,Zeng, Wei,Zhang, Fengtao,Zhao, Yanfei
supporting information, p. 9870 - 9875 (2021/12/27)
Herein, we report a CO2-mediated base catalysis approach for the activation of triple bonds in ionic liquids (ILs) with anions that can chemically capture CO2 (e.g., azolate, phenolate, and acetate), which can achieve hydration of triple bonds to carbonyl chemicals. It is discovered that the anion-complexed CO2 could abstract one proton from proton resources (e.g., IL cation) and transfer it to the CN or CC bonds via a six-membered ring transition state, thus realizing their hydration. In particular, tetrabutylphosphonium 2-hydroxypyridine shows high efficiency for hydration of nitriles and CC bond-containing compounds under a CO2 atmosphere, affording a series of carbonyl compounds in excellent yields. This catalytic protocol is simple, green, and highly efficient and opens a new way to access carbonyl compounds via triple bond hydration under mild and metal-free conditions.
An efficient and recyclable AgNO3/ionic liquid system catalyzed atmospheric CO2 utilization: Simultaneous synthesis of 2-oxazolidinones and α-hydroxyl ketones
Bu, Chao,Chaemchuen, Somboon,Chen, Cheng,Du, Minchen,Gong, Yanyan,Hu, Jia,Verpoort, Francis,Yuan, Ye,Zhang, Yongxing
, p. 70 - 82 (2020/12/21)
Oxazolidinones and α-hydroxyl ketones are two series of fine chemicals that have been generally utilized in biological, pharmaceutical, and synthetic chemistry. Herein, a AgNO3/ionic liquid (IL) catalytic system was developed for the simultaneous synthesis of these compounds through the atom-economical three-component reactions of propargyl alcohols, 2-aminoethanols, and CO2. Notably, this system behaved excellent catalytic activity with the lowermost metal loading of 0.25 mol%. Meanwhile, it is the first reported metal-catalyzed system that could efficiently work under atmospheric CO2 pressure and be recycled at least five times. Evaluation of the green metrics proved the AgNO3/IL-catalyzed processes to be relatively more sustainable and greener than the other Ag-catalyzed examples. Further mechanistic investigations revealed the derivative active species of N-heterocyclic carbene (NHC) silver complexes and CO2 adducts generated during the process. Subsequently, their reactivity in this reaction was assessed for the first time, which was finally identified as beneficial for the catalytic activity.
Thermodynamic favorable CO2 conversion via vicinal diols and propargylic alcohols: A metal-free catalytic method
Han, Li-Hua,Li, Jing-Yuan,Song, Qing-Wen,Zhang, Kan,Zhang, Qian-Xia,Sun, Xiao-Fang,Liu, Ping
supporting information, p. 341 - 344 (2019/07/04)
Organocatalysis represents a promising field in chemical fixation of CO2. Herein, a facile metal-free strategy was reported for the one-pot preparation of cyclic carbonates and α-hydroxy ketones from vicinal diols, propargylic alcohols and CO2. Wide scope of vicinal diols and propargylic alcohols was demonstrated to be efficient under the DBU-catalyzed conditions. A plausible mechanism was proposed, which included detailed main and side reactions under the metal-free conditions.
SUBSTITUTED IMIDAZOLECARBOXYLATE DERIVATIVES AND THE USE THEREOF
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Paragraph 0736-0738, (2020/12/08)
A compound is shown in formula (I). The derivatives of the compound include a stereoisomer, a pharmaceutically acceptable salt, a solvate, a prodrug, a metabolite, a deuterated derivative. The compound is a structurally novel substituted imidazole formate derivative. Substituted imidazole formate derivatives are used in preparing a drug with sedative, hypnotic and/or anesthetic effects, as well as a drug that can control the state of epilepsy. The compound has a good inhibitory effect on the central nervous system, and provides a new option for clinical screening of and/or preparation of a drug with sedative, hypnotic and/or anesthetic effects and controlling the state of epilepsy.
Synthesis of Imidazo[1,2-a]pyridines and Imidazo[2,1-b]thiazoles Attached to a Cycloalkyl or Saturated Heterocycle Containing a Tertiary Hydroxy Substitution
Chenna Reddy,Patil, Vineetkumar B.,Nawaz Khan, Fazlur Rahman,Saravanan, Vadivelu
, p. 1486 - 1497 (2019/04/04)
A new method has been developed for the synthesis of imidazo[1,2-a]pyridines, imidazo[2,1-b]thiazoles, and benzo[d]imidazo[2,1-b]thiazoles attached to a cycloalkyl or saturated heterocycle containing a tertiary hydroxy substitution. Readily available substituted 2-aminopyridines, 2-aminothiazoles, and 2-aminobenzothiazoles were treated with bromohydroxycycloalkyl ethanones to afford the desired products in good yields.
