JOURNAL OF MOLECULAR STRUCTURE
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2024
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IF 4
Qianqian Xing,Xiaoliang Jia,Shiyu Jia,Yongqin Qi,Yuqi Wang,Yingxiong Wang,Xianglin Hou
The traditional synthesis methods of cyclopropyl methyl ketone (CPMK) have some disadvantages such as low yield, slow reaction rate and unclear catalytic mechanism. To solve these problems, a new strategy is developed to synthesize CPMK from 5‑chloro-2-pentanone (CPE) using 1,8-diazabicyclo[5.4.0]undec‑7-ene (DBU). Experiment results show that the yield of CPMK reached a maximum of 96.5 % in DBU at 40 °C for 30min. The mechanism study shows that the hydrogen bond between DBU and CPE is the key to drive the deprotonation and cyclization of CPE. The hydrogen bond is formed between the N atom on C = N of DBU and the α-H on the methylene group associated with the carbonyl group on CPE. The catalyst DBU is converted into [DBUH] + Cl − , which can be reclaimed and recycled completely. The density functional theory (DFT) calculation confirmed the existence of molecular hydrogen bonds and proved that the hydrogen bond driving force is the key to the reaction. The hydrogen bond driven mechanism provides a new idea for the basic research of cyclization reaction.
研究领域:
有机化学
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催化反应
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产品关联
DOI
高影响因子
CyTA-Journal of Food
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2018
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IF 1.371
Liang Li,Ying Ma
Methyl ketones can be formed by the metabolism of intermediate products of β-oxidation by enzymes. In this article, the effect of soluble saccharides on the activity of key enzymes involved in methyl ketone synthesis in L. lactis was studied by detecting the relationship between soluble saccharides and enzyme activity. The results showed that glucose, fructose, sucrose, lactose and galactose could promote the growth of L. lactis. Glucose induced the activity of enoyl-coenzyme A (CoA) hydratase but inhibited the activity of β-hydroxyacyl-CoA dehydrogenase. Fructose induced the activities of acyl-CoA dehydrogenase and enoyl-CoA hydratase while maintaining the activity of β-hydroxyacyl-CoA dehydrogenase. Sucrose induced the activities of enoyl-CoA hydratase and β-hydroxyacyl-CoA dehydrogenase and maintained the activity of thiolase. Lactose also induced enoyl-CoA hydratase activity. Galactose induced enoyl-CoA hydratase activity and maintained thiolase activity. Glucose, lactose, fructose and galactose induced thioesterase activity. The data showed fructose and lactose could inhibit thiolase activity and induce thioesterase activity, which would be beneficial to methyl ketone synthesis, so fructose and lactose were the best soluble saccharides, followed by galactose, glucose and sucrose. A positive and significant correlation was found between thioesterase activity and enoyl-CoA hydratase activity (p < 0.01). In summary, the β-oxidation system of L. lactis is related to sugar metabolism.
研究领域:
微生物学
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生物化学
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DOI
高影响因子
ORGANIC & BIOMOLECULAR CHEMISTRY
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2017
·Vol. 15
·期 16
·3427-3434
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IF 3.564
Dan Wang,Kuan Zhang,Luhan Jia,Danting Zhang,Yue Zhang,Yujia Cheng,Chang Lin,Bo Wang
Presented here is the first example of synthesizing an array of primary-, secondary-, and tertiary-α-ketoamides with a non-metal catalyst nBu4NI from methyl ketones and inexpensive readily available amine/ammonium salts; the reactions proceeded smoothly under mild conditions, TBHP was used as an oxidant and the corresponding α-ketoamides were afforded in moderate to excellent yields.
研究领域:
有机化学
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催化化学
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DOI
PubMed
高影响因子
Cell Reports Physical Science
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2025
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IF 7.3
Yan-Wei Jiang,Zhong-Wei Zhang,Chi Wai Cheung,Jun-An Ma
Trifluoromethyl ketones (TFMKs) represent a crucial class of functional groups in organic synthesis and drug design. Carbo- and heteroatom-substituted methyl TFMKs have been developed extensively, leading to a broad array of structurally diverse trifluoromethylated compounds. However, aminomethyl TFMKs remain largely underexplored, likely due to the intrinsic incompatibility between amino and carbonyl groups. Here, we present a modular strategy for accessing aminomethyl TFMKs in a cyclic acetal-protected form. Using 2-(trifluoromethyl)-1,3-dioxolane-2-carboxylic acid as a masked trifluoroacetyl radical precursor, along with nitroarenes and tertiary alkylamines as readily available reaction components, we demonstrate the feasibility of assembling these compounds under metallaphotocatalytic conditions. This approach selectively yields a diverse array of N -(2-trifluoromethyl)dioxolanylmethyl aniline compounds, which act as inactivated forms of arylaminomethyl TFMKs and can be readily converted into arylaminomethyl TFMKs, various amine derivatives, and azaheterocycles. The structurally distinctive trifluoromethylated dioxolanylmethyl anilines and their downstream products hold significant potential for pharmaceutical and agrochemical development.
研究领域:
有机化学
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药物化学
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合成化学
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DOI
高影响因子
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
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2023
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IF 6.7
Dongliang Guan,Jian Li,Feifei Chen,Jiaqi Li,Xiaolei Bian,Yue Yu,Xinxin Feng,Lefu Lan,Wei Huang
Wide-spread use of daptomycin unavoidably resulted in the emergence of daptomycin-resistant pathogens. In the hunt for more active daptomycin derivatives through medicinal chemistry studies, we established a concise semisynthetic approach to modify the L-Kyn13 on daptomycin specifically and effectively. Here, 19 novel derivatives with certain diversity were designed and synthesized to perform a comprehensive SAR study on this underestimated position. The optimal compound, termed “hexakynomycin”, as the new generation of daptomycin-based antibiotic candidate exhibited 4->125-fold higher activity against methicillin-susceptible S. aureus (MSSA), methicillin-resistant S. aureus (MRSA), vancomycin-intermediate resistant S. aureus (VISA), and vancomycin-resistant Enterococci (VRE), including daptomycin-resistant strains, compared with that of daptomycin. Greater membrane binding capacity rendered hexakynomycin better activity and special antibiotic property. Hexakynomycin also demonstrated a better pharmacokinetic profile, good safety features and good pharmacodynamics properties. This work provided an effective modification strategy aiming at daptomycin which provided significant insights and showed great promise for the next generation of daptomycin derivatives.
研究领域:
医药化学
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微生物学
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感染病学
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产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
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2015
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IF 1.098
Jianguo Yang,Shuo Liu,Huanan Hu,Shibin Ren,Anguo Ying
A simple and efficient method is proposed for the synthesis of tetrahydrobenzo[b]pyrans with aromatic aldehydes, active methylene compounds, and dimedone using basic ionic liquid catalyst in water. The procedure offers several advantages including short reaction time, good yield, easy procedure, and good recyclability of catalysts, which may be a practical alternative to conventional processes for preparation of 4-hpyrans.
研究领域:
有机化学
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绿色化学
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DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
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2025
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IF 6.2
Zhiyun Li,Saili Xu,Menglan Li,Wenhao Xu,Dang Cheng,Zhiran Ju,Fen-Er Chen
Isavuconazole, a clinically important triazole antifungal drug, relies on α-hydroxymethyl ketone as a key synthetic precursor. Here, we present a novel chemo-enzymatic approach for the synthesis of isavuconazole. Using 2,5-difluorobenzaldehyde as the starting material, engineered benzaldehyde lyase (BAL) catalyzes the crucial benzoin reaction to form the key intermediate α-hydroxymethyl ketone. Notably, this biocatalytic process operates without extra cofactors (thiamine pyrophosphate, ThDP) and Mg2+, achieving a time-space yield (TSY) of 17.2 g·L–1·day–1 under optimized conditions. After further chemical reactions on the intermediate, isavuconazole is obtained through an eco-friendly process that outshines traditional chemical synthesis. This optimized protocol is efficient and scalable, yielding isavuconazole at 28.9%, double that of the current industrial chemical process (14.2%), highlighting the remarkable advantages of enzyme-catalyzed synthesis.
研究领域:
药物化学
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生物催化
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合成生物学
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抗真菌药物研发
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绿色制药
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DOI
PubMed
高影响因子
Journal of Sulfur Chemistry
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2022
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IF 2.325
Ling Jiang,Qingqing Lu,Qianqian Huang,Yue Cheng,Xiaohe Chu
In this paper, a simple and environment-friendly protocol was developed for the synthesis of arylsulfonyl 4H-pyrans via L-proline-catalyzed one-pot two-step reaction of aromatic aldehyde with phenylsulphonyl acetonitrile and dimedone under ball-milling conditions. Environmental acceptability, wide substrate scope, low cost and operational simplicity are the key features of this method.
研究领域:
有机化学
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绿色化学
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DOI
高影响因子
Journal of Materials Chemistry C
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2016
·Vol. 4
·期 21
·4662-4667
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IF 5.066
Yu-Mo Zhang,Fuli Xie,Wen Li,Yuyang Wang,Weiran Zhang,Xiaojun Wang,Minjie Li,Sean Xiao-An Zhang
A new multi-stimuli-responsive molecular switch M5 with a methyl ketone bridge has been developed to fabricate a visible-near infrared absorbing electrochromic device. The basochromic and electrochromic properties of methyl ketone M5 with nitronaphthalene were studied in detail using a spectroelectrochemical method and density functional theory (DFT) calculations. The colorless M5 can be switched to green-yellow with broad visible-near infrared absorption (400–500 nm, 550–800 nm), stimulated by base and electricity. And a multi electron transfer–proton transfer mechanism (electrobase) of electrochromism for M5 has been proved using cyclic voltammetry (CV) and in situ UV-vis spectroscopy. This multi-stimuli-responsive color switch has been successfully applied in an electrochromic device with attractive properties such as short switching time and good reversibility.
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
Journal of the American Chemical Society
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2015
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IF 12.113
Xiao-Li Pei,Yang Yang,Zhen Lei,Shan-Shan Chang,Zong-Jie Guan,Xian-Kai Wan,Ting-Bin Wen,Quan-Ming Wang
The activation of C(sp3)–H bonds is challenging, due to their high bond dissociation energy, low proton acidity, and highly nonpolar character. Herein we report a unique gold(I)–silver(I) oxo cluster protected by hemilabile phosphine ligands [OAu3Ag3(PPhpy2)3](BF4)4 (1), which can activate C(sp3)–H bonds under mild conditions for a broad scope of methyl ketones (RCOCH3, R = methyl, phenyl, 2-methylphenyl, 2-aminophenyl, 2-hydroxylphenyl, 2-pyridyl, 2-thiazolyl, tert-butyl, ethyl, isopropyl). Activation happens via triple deprotonation of the methyl group, leading to formation of heterometallic Au(I)–Ag(I) clusters with formula RCOCAu4Ag4(PPhpy2)4(BF4)5 (PPhpy2 = bis(2-pyridyl)phenylphosphine). Cluster 1 can be generated in situ via the reaction of [OAu3Ag(PPhpy2)3](BF4)2 with 2 equiv of AgBF4. The oxo ion and the metal centers are found to be essential in the cleavage of sp3 C–H bonds of methyl ketones. Interestingly, cluster 1 selectively activates the C–H bonds in −CH3 rather than the N–H bonds in −NH2 or the O–H bond in −OH which is traditionally thought to be more reactive than C–H bonds. Control experiments with butanone, 3-methylbutanone, and cyclopentanone as substrates show that the auration of the C–H bond of the terminal methyl group is preferred over secondary or tertiary sp3 C–H bonds; in other words, the C–H bond activation is influenced by steric effect. This work highlights the powerful reactivity of metal clusters toward C–H activation and sheds new light on gold(I)-mediated catalysis.
研究领域:
无机化学
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有机金属化学
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催化
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产品关联
DOI
PubMed
高影响因子
FUEL
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2021
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IF 6.609
Shan Feng,Xinghua Zhang,Qi Zhang,Yuan Liang,Xuelai Zhao,Chenguang Wang,Longlong Ma
Production of aviation fuel is promising but challenging in the field of biomass utilization. Here we proposed a route to produce highly branched alkanes by the self-aldol condensation of methyl isobutyl ketone (MIBK), followed by the one-step hydrodeoxygenation (HDO). The catalytic activities of magnesium-aluminum mixed oxides (MgAl-O) were carefully explored in the self-aldol condensation of MIBK using cyclohexane as the solvent. The basic sites with moderate and strong strength play a key role in the self-aldol condensation of methyl isobutyl ketone, which can capture α-H, promoting the aldol condensation . Under an optimal condition, the yield of condensation product C12 oxygenate is 70.3%. Furthermore, the regeneration ability of 500-MgAl-O catalyst is tested in the self-aldol condensation of MIBK. In addition, hydrodeoxygenation of condensation products was also conducted over 2 wt% Pd/HZSM-5 catalysts. These obtained HDO products are highly branched alkanes with low freezing point (<−60 °C).
研究领域:
化学工程
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催化
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可再生能源
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生物燃料
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产品关联
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
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2024
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IF 3.3
Jin Yan,Suijie Zhong,Xu Chen,Yihuan Luo,Hua Cao,Xiang Liu,Limin Zhao
Here, we report controlled and site-selective C–H alkenylation and dialkenylation of indolizines and pyrrolo[1,2-a]quinolines with β-alkoxyvinyl trifluoromethylketones under simple and practical conditions. Moreover, this direct C–H alkenylation strategy can also be extended to imidazo[1,2-a]pyridines. Notably, without a transition metal and external oxidant, efficient dehydrogenative β-alkenylation of tertiary amines with β-alkoxyvinyl trifluoromethylketones is presented.
研究领域:
有机化学
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合成化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）