Molecular Catalysis
·
2024
·
IF 3.9
Hui Cao,Yu Liu,Yanqiu Li,Yingxiong Wang,Yan Qiao
The α-hydroxyketones and 1,2-diols are versatile building blocks for the preparation of many natural and synthetic bioactive compounds. In this study, N-heterocyclic carbon (NHC) promoted coupling of several aldehydes with formaldehyde enabled the synthesis of 1,2-diols in moderate to high yields. The highly selective conversion of several aldehydes and formaldehyde into 1,2-diols and α-hydroxyketones was achieved in a one-pot two-step process via [BHMIm][OAc] as a key intermediate. In the first step, formaldehyde was quantitatively converted to [BHMIm][OAc] through the carbene addition. In the second step, 1,2-diol was produced through the intermediate-promoted aldol reaction. The results showed that benzaldehyde was capable to react with [BHMIm][OAc] efficiently, with a 54.1% yield of 1,2-diol after the 3-hour reaction at 85 °C. Among the tested benzaldehyde derivatives, the 4-nitrobenzaldehyde showed the highest yield of 1,2-diol (73.3%) under the optimized reaction conditions. Incorporation of an electron rich group on benzaldehyde promoted carbene regeneration. With 4-methoxybenzaldehyde as the substrate, the yield of α-hydroxyketone reached a maximum of 30.6%. Additionally, dihydroxyacetone derivatives were detected in the system. In situ NMR technique confirmed that it was generated from the further reaction of the carbene/1,2-diol complex with another aldehyde. Based on the results of NMR spectroscopy and mass spectrometry, a possible reaction pathway was also proposed.
研究领域:
有机化学
·
合成化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2019
·
IF 4.914
Zhi-Hua Zhou,Xiao Zhang,Yong-Fu Huang,Kai-Hong Chen,Liang-Nian He
Inexpensive and efficient Cu(I) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO 2 , and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO 2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO 2 as a crucial cocatalyst under mild conditions.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2023
·
IF 5.2
Xiaoxuan Guo,Fenglei Zhang,Yaseen Muhammad,Zhixiu Yang,Ruiping Wei,Lijing Gao,Guomin Xiao
The conversion of CO 2 into high value-added chemicals through efficient catalysis is an ideal strategy to reduce atmospheric CO 2 pollution and achieve carbon neutrality . Therefore, amino-functionalized organic polymer Cu@Co-PIL-N 4 loaded with highly dispersed CuI as a novel catalyst was developed. The functionalization of the surface and the high dispersion of the active phase integrate CO 2 capture and conversion into one catalytic system. The locally enriched CO 2 is converted to the easily activated carbon-oxygen negative ion by the action of primary or secondary amines. Thus, it is easier to achieve efficient preparation of α-alkylidene cyclic carbonates (STY = 20.8 h −1 ) by CO 2 carboxylative cyclization under mild conditions (25 °C, CO 2 pressure of 1 bar). The addition of a small amount of water to the cyclization system boosted domino reaction to convert the α-alkylidene cyclic carbonates to α-hydroxy ketones. The domino reaction also exhibited efficient catalytic activity and outstanding regioselectivity. In addition, the Cu@Co-PIL-N 4 catalyst exhibited excellent substrate expansion and cyclic regeneration for both reactions. This work promises great significance for further developing cost-effective and high-performance catalysts for the chemical conversion of CO 2 .
研究领域:
化学工程
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催化科学
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环境科学
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
·
2024
·Vol. 26
·期 1
·62
·
IF 4.9
Yuankun Wang,Chongli Wang,Weidong Lin,Qin Wang,Baisong Li,Cheng Chen,Ye Yuan,Francis Verpoort
α-Hydroxy ketones are a crucial class of organic compounds prevalent in natural products and pharmaceutical molecules. The CO2-promoted hydration of propargylic alcohols is an efficient method for the synthesis of α-hydroxy ketones. Herein, an ionic liquid (IL) was designed to catalyze this reaction individually under atmospheric CO2pressure, volatile organic solvents, and additives. This IL, constructed from the molybdate anion, can be recycled from industrial (NH4)2MoO4production wastewater, demonstrating its high tolerance to catalytic environments and significant potential for practical applications. To our knowledge, this is the first instance of an oxometallate-based IL catalyst being utilized for the CO2-promoted hydration of propargylic alcohols. Further mechanistic studies revealed the bifunctionality of this IL in activating both CO2and substrates.
研究领域:
有机化学
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催化化学
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绿色化学
✓ 已验证
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Wenwen Pei,Xuewen Zhang,Yan Zeng,Jiao Li,Ziyi Li,Jiangang Yang,Xinjun Du,Yueming Zhu,Yuanxia Sun
α-Hydroxyketones, which have significant industrial applications, can be sustainably synthesized through the oxidation of secondary alcohols using secondary alcohol dehydrogenase (SADH). However, the activity of the SADH oxidation reaction is generally low, making it unsuitable for large-scale production. In this study, a rational design approach was employed to computationally engineer SADH derived from Ogataea parapolymorpha ( Op SADH), significantly enhancing its oxidation activity towards ( R )-1,2-propanediol (PDO). The mutant M2 (S222T/S316A) exhibited a 14.2-fold increase in specific enzyme activity compared to the wild type (WT) and was employed as a catalyst for high-concentration hydroxyacetone production, facilitated by an NAD + regeneration system. By applying an appropriate Zn 2+ ion force field in molecular dynamics (MD) simulations, it was found that two mutation sites could stabilize the conformations of NAD + and PDO, thereby revealing the molecular mechanism behind the enhanced activity of this metalloenzyme mutant. Notably, we first uncovered the dynamic mechanism by which four key residues (Cys39, His75, Glu76, and Glu175) and PDO within the active pocket contribute to the formation of coordination bonds with Zn 2+ . The findings of this study provide robust support for researching the catalytic mechanisms and dynamics processes of metalloenzymes.
研究领域:
生物化学
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酶工程
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计算生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2020
·
IF 7.632
Di Li,Yanyan Gong,Minchen Du,Chao Bu,Cheng Chen,Somboon Chaemcheun,Jia Hu,Yongxing Zhang,Ye Yuan,Francis Verpoort
α-Hydroxy ketones are a series of biologically active fragments in nature as well as important synthons for organic chemistry. Herein, an AgOAc/1-ethyl-3-methylimidazolium acetate ionic liquid system was developed for the CO2-promoted hydration of propargylic alcohols and H2O to produce α-hydroxy ketones. Diverse desired products could be obtained in satisfactory yields under 1 bar of CO2 pressure with the catalysis of only a trace amount of silver (0.005–0.25 mol %), which is the lowest level ever reported for the metal-catalyzed systems. In particular, this system had robust recyclability, and it could be reused effectively at least 5 times. Furthermore, an unprecedented turnover number (TON) of 9200 was achieved, which is considered to be the highest TON ever reached for this hydration.
研究领域:
有机化学
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催化
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2021
·
IF 7.92
Ye Yuan,Jia Hu,Yu Wang,Leilei Huang,Jiayun Zheng,Yufeng Zhao,Yiyun Chen,Cheng Chen,Francis Verpoort
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 CO 2 -promoted hydration process of propargyl alcohols, which was catalyzed by a system consisted of economical CuSO 4 ·5H 2 O and a green 1-butyl-3-methylimidazolium acetate ionic liquid. Particularly, this catalytic system exhibited excellent activity under atmospheric CO 2 or even mimetic flue gas (20 vol% of CO 2 ). 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%.
研究领域:
催化
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绿色化学
·
有机合成
✓ 已验证
DOI
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 45
·e202404657
·
IF 1.9
Chenyue Zhao,Heran Yang,Shuo Hu,Yaqian Liu,Dongping Cheng,Xiaoliang Xu
Graphical In the presence of CBrCl3 and ruthenium photocatalyst, the corresponding dione was obtained by visible light induced oxidation of α-hydroxyl ketone derivatives with the yield of 49%–95%. It has the advantages of medium to excellent yield, good functional group tolerance, and mild reaction conditions. A visible light-induced oxidation of α-hydroxy ketone derivatives is reported, which is carried out in the presence of CBrCl 3 and ruthenium photocatalyst, and the corresponding diketones are obtained in 49-95% yields. This reaction has the advantages of moderate to excellent yields, good functional group tolerance, and mild reaction condition. The free radical reaction process was confirmed by the addition of radical scavenger 2,2,6,6-tetramethylpiperidi-1-oxy (TEMPO). The fluorescence quenching experiment indicated that CBrCl 3 was participated in the oxidation quenching cycle.
研究领域:
有机化学
·
光化学
·
合成化学
✓ 已验证
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2020
·
IF 7.888
Minchen Du,Yanyan Gong,Chao Bu,Jia Hu,Yongxing Zhang,Cheng Chen,Somboon Chaemchuen,Ye Yuan,Francis Verpoort
Oxazolidinones and α-hydroxyl ketones are two series of fine chemicals that have been generally utilized in biological, pharmaceutical, and synthetic chemistry. Herein, a AgNO 3 /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 CO 2 . 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 CO 2 pressure and be recycled at least five times. Evaluation of the green metrics proved the AgNO 3 /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 CO 2 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.
研究领域:
催化
·
绿色化学
·
有机合成
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）