1123-27-9Relevant articles and documents
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.
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Newman,M.S.,Lee,V.
, p. 381 - 382 (1975)
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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..
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.
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.
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.
