- Enecarbamates as imine surrogates: Nucleophilic addition of 1,3-dicarbonyl compounds to enecarbamates
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(Chemical Equation Presented) Novel Mannich-type reactions of 1,3-dicarbonyl compounds with enecarbamates have been developed. Stable and storable enecarbamates work as surrogates of aliphatic aldehyde-derived imines, which are known to be difficult to isolate and store.
- Kobayashi, Shu,Gustafsson, Tomas,Shimizu, Yusuke,Kiyohara, Hiroshi,Matsubara, Ryosuke
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- Highly Selective Difluoromethylations of β-Keto Amides with -TMSCF 2Br under Mild Conditions
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Without employing any transition metal and other additives, efficient methods for selective difluoromethylations of β-keto amides with TMSCF 2 Br reagent have been developed under mild conditions. This protocol allows a convenient access to various α-difluoromethyl β-keto amides with excellent yields (up to 93%) and high carbon/oxygen (C/O) regioselectivities (up to 99:1). The C/O selectivity of β-keto amides could be easily reversed and controlled by simply changing the base. This protocol can be easily scaled-up and the C-difluoromethylation product could be reduced into CF 2 H-containing amino alcohol derivatives. Moreover, the first enantioselective electrophilic difluoromethylation of β-keto amides has been achieved by phase-transfer catalysis.
- Chen, Pengli,Fu, Yang,Hu, Yanqin,Wang, Shuaifei,Wang, Yakun,Zhang, Conghui,Zhang, Mingwei,Zhao, Ting
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supporting information
p. 1123 - 1130
(2021/06/18)
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- Method for synthesizing methyl 6-chloro-3-oxo-1,2-dihydroindene-2-carboxylate by one-pot method
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The invention discloses a method for synthesizing methyl 6-chloro-3-oxo-1,2-dihydroindene-2-carboxylate by one-pot method, thereby overcoming the technical defects of long synthesis route, multiple reaction steps, multiple generated three wastes, high difficulty in subsequent three waste treatment and the like in the prior art. methyl 6-chloro-3-oxo-1,2-dihydroindene-2-carboxylate is synthesizedfrom a substrate parachlorobenzoyl chloride and methyl acrylate by a one-pot method under the effect of lewis acid. A one-pot synthesis reaction is adopted, the reaction steps are few, operation is easy, raw materials are easy to obtain, and the method is economical, environmentally friendly and suitable for the current environmental protection requirement.
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Paragraph 0019-0028
(2020/10/20)
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- Ring-Strain-Enabled Catalytic Asymmetric Umpolung C-O Bond-Forming Reactions of 1,2-Oxazetidines for the Synthesis of Functionalized Chiral Ethers
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An unprecedented catalytic asymmetric umpolung C-O bond-forming reaction of N-nosyl 1,2-oxazetidines with β-keto esters has been achieved in the presence of a chiral phase-transfer catalyst, allowing access to a range of highly functionalized chiral ethers bearing quaternary and no adjacent stereogenic centers with high yields, excellent enantioselectivities, and diastereoselectivities (up to 97percent ee and 20:1 dr). These versatile products could be flexibly transformed into biologically important chiral fused and spiro morpholines in two steps.
- Wu, Binyu,Yang, Jinggang,Gao, Min,Hu, Lin
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supporting information
p. 5561 - 5566
(2020/07/14)
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- Highly Carbon-Selective Monofluoromethylation of β-Ketoesters with Fluoromethyl Iodide
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A highly carbon-selective monofluoromethylation of a broad range of β-ketoesters with fluoromethyl iodide under mild conditions is described. The uses of lithium tert-butoxide as the base and diglyme as the solvent made great contributions to the high C/O regioselectivity.
- Ding, Tianqi,Jiang, Lvqi,Yang, Jie,Xu, Yimin,Wang, Guixiang,Yi, Wenbin
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supporting information
p. 6025 - 6028
(2019/08/20)
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- Discovery of a Novel Series of Tricyclic Oxadiazine 4a-Methyl Esters Based on Indoxacarb as Potential Sodium Channel Blocker/Modulator Insecticides
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Indoxacarb, a commercialized oxadiazine insecticide, nearly irreversibly blocks open/inactivated, but not resting sodium channels. The structure-activity relationships showed that the substituents at the position of the chiral atom in the oxadiazine ring are very important to the biological activity of oxadiazine insecticide. Here we synthesized a series of tricyclic oxadiazine 4a-methyl ester derivatives. The chiral atom in the oxadiazine ring has been epimerized and substituted with either pyrethric acid or cinnamic acid derivatives. Benzene ring in the tricyclic moiety was substituted with a chlorine, fluorine, or bromine atom, and nitrogen-linked benzene ring was substituted with a trifluoromethyl or trifluoromethoxy group. Toxicity of these compounds against Spodoptera litura F. was evaluated. Diastereoisomers of most toxic compounds J7 and J9 with pyrethric acid moiety were separated by flash column chromatography. The more polar diastereoisomers, J7-L-Rf and J9-L-Rf, and compounds J24 and J26 with cinnamic acid moiety exhibited highest insecticidal activities. We further used Monte Carlo energy minimizations to dock compound J7 and J24 in the NavMs-based homology model of the open cockroach sodium channel. In the low-energy binding modes, the compound interacted with residues in the inner pore and domain interfaces, which previously were proposed to contribute to receptors of pyrethroids and sodium channel blocker insecticides. Our results define compound J7 and J24 as a potentially useful optimized hit for the development of multiple sites sodium channel blocker or modulator.
- Zhang, Jianqiang,Hao, Wenbo,Zhorov, Boris S.,Dong, Ke,Jiang, Dingxin
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p. 7793 - 7809
(2019/08/01)
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- Whole-cell biocatalytic of Bacillus cereus WZZ006 strain to synthesis of indoxacarb intermediate: (S)-5-Chloro-1-oxo-2,3-dihydro-2-hydroxy-1H-indene-2-carboxylic acid methyl ester
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In this study, a newly isolated strain screened from the indoxacarb-rich agricultural soils, Bacillus cereus WZZ006, has a high stereoselectivity to racemic substrate 5-chloro-1-oxo-2,3-dihydro-2-hydroxy-1H-indene-2-carboxylic acid methyl ester. (S)-5-chloro-1-oxo-2,3-dihydro-2-hydroxy-1H-indene-2-carboxylic acid methyl ester was obtained by bio-enzymatic resolution. After the 36-hour hydrolysis in 50-mM racemic substrate under the optimized reaction conditions, the e.e.s was up to 93.0% and the conversion was nearly 53.0% with the E being 35.0. Therefore, B cereus WZZ006 performed high-level ability to produce (S)-5-chloro-1-oxo-2,3-dihydro-2-hydroxy-1H-indene-2-carboxylic acid methyl ester. This study demonstrates a new biocatalytic process route for preparing the indoxacarb chiral intermediates and provides a theoretical basis for the application of new insecticides in agricultural production.
- Zhang, Yinjun,Zhang, Hongyun,Cheng, Feifei,Xia, Ying,Zheng, Jianyong,Wang, Zhao
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p. 958 - 967
(2019/09/03)
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- Oxadiazine cinnamate derivatives as well as preparation method and application thereof
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The invention provides oxadiazine cinnamate derivatives as well as a preparation method and application thereof. The molecular structures of the oxadiazine cinnamate derivatives are shown in a formula(I) described in the description, wherein R1 is hydrogen, halogen, an alkyl group having 1-4 carbon atoms, alkoxy having 1-4 carbon atoms or an amino group; R2 is -CF3, -OCF3 or -OCH2F. The preparation method provided by the invention combines indoxacarb with cinnamic acid so as to obtain the oxadiazine cinnamate derivatives by rationally designing the structure of the indoxacarb; the oxadiazinecinnamate derivatives not only can significantly increase the poisonous activity of prodenia litura, but also has good biological activity against mosquitoes with drug resistance; compared with commercial indoxacarb insecticide, the poisonous activity of the compounds against pests is greatly enhanced, and the biological activity of the compounds for drug-resistant pests is especially enhanced, sothat drug protection is provided for the prevention and control of the resistant pests. Furthermore, the raw materials used in the method for producing the compounds provided by invention are readilyavailable, the reaction conditions are mild, and the yield of the target product is high.
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Paragraph 0052-0055
(2018/07/30)
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- Method for catalytic oxidation of indanone-2-formate under micro-reaction conditions or conventional reaction conditions
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The invention provides a method for catalytic oxidation of indanone-2-formate under micro-reaction conditions or conventional reaction conditions, belonging to the technical field of organic chemicalsynthesis. The method comprises the following steps: mixing the indanone-2-formate, a catalyst and a solvent so as to obtain a homogeneous solution; dissolving an oxidizing agent with a solvent, and carrying out extraction and drying so as to obtain a homogeneous solution; allowing two above-mentioned homogeneous solutions to react under the micro-reaction conditions or the conventional reaction reactions so as to obtain a reaction solution; and adjusting the pH value of the above-mentioned reaction solution to 6.5 to 7.5 with hydrochloric acid with a mass fraction of 10%, carrying out stirring for 20 to 30 minutes, then carrying out cooling to 5 DEG C or below, carrying out filtering, flushing a filter cake with a solvent with a temperature of 0 to 5 DEG C, and carrying out drying so as to obtain the indanone-2-hydroxy-2-formate. According to the invention, by utilization of the highly-efficient thermal mass transfer ability of a microchannel reactor, and combination of combined catalytic oxidation of chiral phosphorylimidic acid and organic base, compared with a conventional preparation method, the method provided by the invention has excellent effects of simple process operation, high catalytic oxidation efficiency, short reaction time, simple equipment, high safety and obtainment of a product with high chiral purity.
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Paragraph 0034-0036
(2018/11/27)
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- Highly Enantioselective α-Cyanation with 4-Acetylphenyl Cyanate
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A highly effective asymmetric version of α-cyanation of β-keto esters and amides was developed with a Lewis-acid catalyst. Thus, by using 10 mol % of a tridentate bisoxazoline–zinc(II) complex as the catalyst, a series of chiral nitriles containing a quaternary carbon center were obtained in excellent enantioselectivities (up to 97 % enantiomeric excess) and up to 95 % yield in the presence of 4 ? molar sieve at room temperature. For the first time, mild and active 4-acetylphenyl cyanate was used instead of cyano-hyperiodinate as the cationic cyano source for catalytic asymmetric α-cyanation.
- Qiu, Jia-Shen,Wang, Yao-Feng,Qi, Gui-Rong,Karmaker, Pran G.,Yin, Hong-Quan,Chen, Fu-Xue
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supporting information
p. 1775 - 1778
(2017/02/15)
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- Chiral N,N'-Dioxide Organocatalyzed Asymmetric Electrophilic α-Cyanation of β-Keto Esters and β-Keto Amides
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An enantioselective electrophilic α-cyanation of 1-indanone-derived β-keto esters and β-keto amides using a hypervalent iodine as the cyanide-transfer reagent was realized. A chiral N,N'-dioxide was used as the efficient bifunctional organocatalyst in the presence of inorganic base, which gave the corresponding α-cyano dicarbonyl compounds in yields of 50-99% with good enantioselectivities (87-97% ee).
- Ma, Baiwei,Lin, Xiaobin,Lin, Lili,Feng, Xiaoming,Liu, Xiaohua
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p. 701 - 708
(2017/04/26)
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- Enantioselective electrophilic cyanation of β-keto amides catalysed by a cinchona organocatalyst
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An operationally simple protocol for the enantioselective electrophilic α-cyanation of β-keto amides catalyzed by cinchona-derived catalysts has been demonstrated. The resulting products could be obtained with good to high enantioselectivities (up to 88% ee) and with excellent yields (up to 94%) by employing the mild active 4-acetylphenyl cyanate as the cationic cyano source in the catalytic asymmetric α-cyanation reaction.
- Karmaker, Pran Gopal,Qiu, Jiashen,Wu, Di,Reng, Mengmeng,Yang, Zhuo,Yin, Hongquan,Chen, Fu-Xue
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supporting information
p. 7753 - 7757
(2017/10/06)
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- Oxadiazine derivative, and preparation method and application thereof
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The invention discloses an oxadiazine derivative, and a preparation method and an application thereof. The oxadiazine derivative has a molecular structure as shown in a formula (I) described in the specification. The invention provides the preparation method of the oxadiazine derivative, and the application of the oxadiazine derivative in preparation of pesticides used for prevention and treatment of agricultural or sanitary pests or in preparation of pharmaceutical preparations used for prevention and treatment of animal parasites. The oxadiazine derivative provided by the invention contains two pharmacophores with different action modes to insect sodium ion channels, can reach the purpose of synergistic interaction, shows higher biological activity to pests, can achieve the purpose of increasing prevention and treatment spectrum, and has broad application prospects.
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Paragraph 0095
(2018/04/01)
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- Preparation method of (+)methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate
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The invention relates to the field of pesticide synthesis, and in particular provides a preparation method of an intermediate of indoxacarb, namely (+)methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate, and 5-chloro-1-indanone, dimethyl carbonate, sodium hydride, cumene hydroperoxide and cinchonine are mainly adopted as reactants, and a double dropping way of the cumene hydroperoxide and 5-chloro-2-methoxycarbonyl group-1-indanone is adopted, the disadvantages in the prior art of low yield and low content of S-isomer are changed, the yield is improved, the cost is reduced, and the content of an effective body is improved.
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Paragraph 0019-0020
(2017/03/14)
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- Trimethylchlorosilane-Mediated Mild α-Chlorination of 1,3-Dicarbonyl Compounds Promoted by Phenyliodonium Diacetate
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Trimethylchlorosilane was used as chlorine source for the α-chlorination of 1,3-dicarbonyl compounds with phenyliodonium diacetate as oxidant at room temperature. The reaction allows the selective synthesis of α-monochlorinated products from different kinds of 1,3-dicarbonyl compounds in good yield. The potential possibility of this conversion for bromination has also been investigated.
- Chong, Siying,Su, Yingpeng,Wu, Lili,Zhang, Weigang,Ma, Junyan,Chen, Xiaowei,Huang, Danfeng,Wang, Ke-Hu,Hu, Yulai
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supporting information
p. 1359 - 1370
(2016/05/02)
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- Photo-organocatalytic enantioselective perfluoroalkylation of β-ketoesters
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The visible-light-driven, phase-transfer-catalyzed, enantioselective perfluoroalkylation and trifluoromethylation of cyclic β-ketoesters is described. The photo-organocatalytic process, which occurs at ambient temperature and under visible light illumination, is triggered by the photochemical activity of in situ-generated electron donor-acceptor complexes, arising from the association of chiral enolates and perfluoroalkyl iodides. Preliminary mechanistic studies are reported.
- Wo?niak, ?ukasz,Murphy, John J.,Melchiorre, Paolo
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supporting information
p. 5678 - 5681
(2015/05/20)
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- Bifunctional Thiourea Catalyzed Asymmetric Mannich Reaction Using Trifluoromethyl Aldimine as Trifluoromethyl Building Blocks
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An efficient bifunctional thiourea catalyzed asymmetric Mannich reaction with trifluoromethyl aldimine as trifluoromethyl building block was achieved to give the products in good diastereoselectivity and enantioselectivity.
- Ji, Shilong,Alkhalil, Ahmed Ebrahim,Su, Yingpeng,Xia, Xiaowen,Chong, Siying,Wang, Ke-Hu,Huang, Danfeng,Fu, Ying,Hu, Yulai
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supporting information
p. 1725 - 1731
(2015/07/20)
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- Design, synthesis and structure-activity relationship of indoxacarb analogs as voltage-gated sodium channel blocker
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Indoxacarb, the first commercialized pyrazoline-type sodium-channel blocker, is a commonly used insecticide because of high selectivity. To discover sodium-channel blocker with high insecticidal activity, a series of novel indoxacarb analogs were designed and synthesized by judicious structural modifications of the substituent group of C5, C6 in indenone and C′4 in benzene ring. Some analogs exhibited significant insecticidal activities against Spodoptera litura F. and excellent BgNav1-1a channel inhibitory activity. The structure-activity analysis indicated that the presence of strong electron-withdrawing group and decreased steric hindrance of indenone ring (R1, R2) in 5- and 6-position could enhance larvicidal activity and BgNav1-1a channel inhibitory activity.
- Hao, Wenbo,Fu, Chunling,Yu, Huijuan,Chen, Jian,Xu, Hanhong,Shao, Guang,Jiang, Dingxin
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supporting information
p. 4576 - 4579
(2015/10/12)
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- Highly efficient C-H hydroxylation of carbonyl compounds with oxygen under mild conditions
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A transition-metal-free Cs2CO3-catalyzed α-hydroxylation of carbonyl compounds with O2 as the oxygen source is described. This reaction provides an efficient approach to tertiary α-hydroxycarbonyl compounds, which are highly valued chemicals and widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very environmentally friendly and practical. This transformation is highly efficient and highly selective for tertiary C(sp3)-H bond cleavage. OH, so simple! A transition-metal-free Cs2CO 3-catalyzed α-hydroxylation of carbonyl compounds with O 2 provided a variety of tertiary α-hydroxycarbonyl compounds (see scheme; DMSO=dimethyl sulfoxide), which are widely used in the chemical and pharmaceutical industry. The simple conditions and the use of molecular oxygen as both the oxidant and the oxygen source make this protocol very efficient and practical.
- Liang, Yu-Feng,Jiao, Ning
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supporting information
p. 548 - 552
(2014/01/23)
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- Catalytic asymmetric cross-dehydrogenative coupling: Activation of C-H bonds by a cooperative bimetallic catalyst system
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A cooperative bimetallic catalyst system was applied in the catalytic asymmetric cross-dehydrogenative coupling of β-ketoesters and xanthene. Various optically active xanthene derivatives bearing a quaternary stereogenic carbon center were obtained in moderate to good yields (up to 90%) with excellent enantioselectivities (up to 99% ee). Meanwhile, a transition-state model was proposed to explain the origin of the asymmetric induction.
- Cao, Weidi,Liu, Xiaohua,Peng, Ruixue,He, Peng,Lin, Lili,Feng, Xiaoming
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p. 3470 - 3472
(2013/05/23)
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- Improved preparation of 5-chloro-2-methoxycarbonyl-1-indanone for total synthesis of indoxacarb
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5-Chloro-2-methoxycarbonyl-1-indanone 1 is an important intermediate for the synthesis of arthropodicidal oxadiazines indoxacarb. Here a convenient and environmentally friendly method with higher yield and low cost compared to existing method was developed. This method could be useful in manufacturing of indoxacarb, lowering the costs and avoiding excessive pollution.
- Zhang, Lingzi,Zhang, Jiafu,Sun, Dequn
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p. 1413 - 1414
(2012/10/07)
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- SUBSTITUTED FLUOROETHYL UREAS AS ALPHA 2 ADRENERGIC AGENTS
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Therapeutic compounds, and methods, compositions, and medicaments related thereto are disclosed herein.
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Page/Page column 30
(2008/12/04)
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- Construction of quaternary stereocenters by efficient and practical conjugate additions to α,β-unsaturated ketones with a chiral organic catalyst
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(Chemical Equation Presented) Added value: The conjugate addition of cyclic or acyclic α-substituted β-ketoesters to α,β-unsaturated ketones using a chiral organic catalyst (1) can be achieved with good enantioselectivity, diastereoselectivity, and yield. This asymmetric C-C bond formation strategy provides a range of chiral building blocks 2 that contain an all-carbon quaternary stereocenter.
- Wu, Fanghui,Li, Hongming,Hong, Ran,Deng, Li
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p. 947 - 950
(2007/10/03)
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- ASYMMETRIC MICHAEL AND ALDOL ADDITION USING BIFUNCTIONAL CINCHONA-ALKALOID-BASED CATALYSTS
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One aspect of the present invention relates to quinine-based and quinidine-based catalysts. Another aspect of the invention relates to a method of preparing a derivatized quinine-based or quinidine-based catalyst comprising 1) reacting quinine or quinidine with 5 base and a compound that has a suitable leaving group, and 2) converting the ring methoxy group to a hydroxy group. Another aspect of the present invention relates to a method of preparing a chiral, non-racemic compound from a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral ketone, comprising the step of: reacting a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral 10 ketone with a nucleophile in the presence of a catalyst; thereby producing a chiral, non racemic compound; wherein said catalyst is a derivatized quinine or quinidine. Another aspect of the present invention relates to a method of kinetic resolution, comprising the step of reacting racemic chiral alkene with a nucleophile in the presence of a derivatized quinine or quinidine.
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Page/Page column 125
(2008/06/13)
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- Novel acid halide derivatives, their production, and production of indanonecarboxylic acid esters using the same
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Disclosed is a novel acid halide derivative represented by Formula (I): wherein X and Y may be the same or different and are each a halogen atom; and R is a lower alkyl group. By cyclizing the acid halide derivative of Formula (I) in the presence of a catalyst, an indanonecarboxylic acid ester represented by Formula (VI): wherein X and R are as defined above, is produced. Such indanonecarboxylic acid esters are useful as intermediates for insecticides.
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- Novel malonic acid monomethyl derivatives and production process thereof
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A novel monomethyl malonate derivative is represented by following Formula (I): wherein X is a halogen atom; and Me is methyl group. This compound can be prepared by the steps of (A) reacting a benzyl halide derivative represented by following Formula (II): wherein X and Y may be the same as or different from each other and are each a halogen atom, with dimethyl malonate in the presence of a base to yield a dimethyl malonate derivative represented by following Formula (III): wherein X and Me have the same meanings as defined above; and (B) hydrolyzing the dimethyl malonate derivative of Formula (III). The compound is useful in the production of an indanonecarboxylic acid ester having a halogen atom on the indanone ring.
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Page/Page column 5
(2008/06/13)
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- Preparation of arthropodicidal oxadiazines
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A method for making arthropodicidal oxadiazines and intermediates which are racemic or enantiomerically enriched at their chiral center, the method for making the oxadiazines comprising reaction of an intermediate selected from STR1 wherein: R1 is F, Cl, or C1 -C3 fluroalkoxy, R2 is C1 -C3 alkyl, and R4 is H or CO2 CH2 (C6 H5). as well as certain selected intermediates including those depicted above, and methods of making them.
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- Process for preparing 2-carboalkoxy-1-indanones
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A process for the preparation of 2-carboalkoxy-1-indanones of Formula I from 1-indanones of Formula II using a dialkyl carbonate and an alkali metal alkoxide is provided. This process is superior to the prior art in that it avoids pyrophoric reagents such as sodium hydride, and proceeds in high chemical yield and product quality. The invention provides a novel process to an important intermediate in the preparation of arthropodicidal carboxanilides of commercial interest. STR1 wherein: R1, R2 and M are defined in the specification.
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- Dihydropyridazinones, pyridazinones and related compounds as fungicides
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This invention relates to substituted dihydropyridazinones, pyridazinones and related compounds, of the formula STR1 wherein A, Q, D and R1 are as defined within, compositions containing these compounds and methods of controlling agricultural and mammalian fungal diseases.
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- Potential hypocholesteremic derivatives of styrylacetic acid II: cis- and trans-3-methyl-4-phenyl-3-butenoic acid analogs.
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The synthesis and preliminary biological testing for in vitro cholesterol biosynthesis inhibitory activity of 2-indeneacetic acid, 2-methyl-1,2-dihydro-2-naphthoic acid, and their 5- and 7-chloro derivatives, respectively are described. These compounds were prepared as trans- and cis-analogs of the known antilipemic agent 3-methyl-4-phenyl-3-butenoic acid. Although both series of compounds showed cholesterol biosynthesis inhibitory properties, chloro substitution enhanced potency only in the cis-system. These findings are discussed in terms of a possible relationship between the cis-compounds and clofibrate-type antilipemic agents.
- Stratford,Smith,Tomecko
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