- Unraveling two pathways for NHPI-mediated electrocatalytic oxidation reaction
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Two pathways for N-hydroxyphthalimide (NHPI)-mediated electrocatalytic oxidation using phenylacetate derivatives as template substrates were first reported for benzylic C[sbnd]H oxidation to oxygenated and non-oxygenated products. DFT calculation indicates that the hydrogen-atom transfer (HAT) process between phthalimido-N-oxyl (PINO) and substrate is a rate-determined step. Aromatic α-keto esters and 2-((1,3-dioxoisoindolin-2-yl)oxy)-2-aryl acetate obtained by cross-coupling between benzylic radical and PINO can be selectively synthesized through controlling the concentration of PINO radical. This method provides a deep understanding for selective weak C[sbnd]H oxidation using NHPI as redox mediator.
- Xu, Leitao,Yi, Yangjie,Hu, Sideng,Ye, Jiao,Hu, Aixi
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- Tandem Photoredox-Chiral Phosphoric Acid Catalyzed Radical-Radical Cross-Coupling for Enantioselective Synthesis of 3-Hydroxyoxindoles
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A photochemical protocol that couples diarylamines and α-ketoesters to afford the chiral 3-hydroxyoxindoles through tandem photoredox and chiral phosphoric acid catalysis is developed. The reaction involves an enantioselective photochemical radical-radical cross-coupling process. The chiral phosphoric acid is discovered to play crucial roles by decreasing the reductive potentials of α-ketoesters and stereocontrolling the downstream asymmetric radical-radical cross-coupling via the formation of pentacoordinate complex.
- Zhang, Yang,Ye, Dan,Shen, Lei,Liang, Kangjiang,Xia, Chengfeng
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supporting information
p. 7112 - 7117
(2021/09/14)
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- Visible-Light-Induced Catalyst-Free Carboxylation of Acylsilanes with Carbon Dioxide
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Intermolecular carbon-carbon bond formation between acylsilanes and carbon dioxide (CO2) was achieved by photoirradiation under catalyst-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of the acylsilanes added to the C═O bond of CO2 to give α-ketocarboxylates, which underwent hydrolysis to afford α-ketocarboxylic derivatives in good yields. Control experiments suggest that the generated siloxycarbene is likely to be from the singlet state (S1) of the acylsilane and the addition to CO2 is not in a concerted manner.
- Fan, Zhengning,Yi, Yaping,Chen, Shenhao,Xi, Chanjuan
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supporting information
p. 2303 - 2307
(2021/04/05)
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- Novel synthesis method of alpha-carbonyl acid ester
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The invention discloses a novel synthesis method of alpha-carbonyl acid ester. The method comprises the following steps: carrying out chlorination reaction on an alpha-methylene-containing nitrile compound and chlorine to obtain dichloronitrile, reacting the dichloronitrile product in a sulfuric acid and water system to obtain formyl cyanide, then acquiring an imino sulfate compound in the same reaction system, and finally performing esterification to obtain the target product. The adopted reaction raw materials are wide in sources and low in price, highly toxic solid sodium cyanide can be prevented from being used in the prior art, the method is environmentally friendly, and the method is easy to operate, mild in condition and easy to industrialize.
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- Method for preparing spiro beta-lactam
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The invention discloses a method for preparing spiro beta-lactam. The method comprises the following step: carrying out [2+1] cyclization reaction on beta-lactam and keto ester under the condition ofa phosphine catalyst to generate spiro beta-lactam. The
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Paragraph 0048-0051
(2020/07/12)
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- Cobalt-Catalyzed Transfer Hydrogenation of α-Ketoesters and N-Cyclicsulfonylimides Using H2O as Hydrogen Source
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A Co-catalyzed effective transfer hydrogenation of various α-ketoesters and N-cyclicsulfonylimides by safe and environmentally benign H2O as hydrogen source is described. The reaction used easily available and easy to handle zinc metal as a reductant. Interestingly, the catalytic system does not require ligand for reduction of N-cyclicsulfonylimides. (Figure presented.).
- Gao, Yang,Zhang, Xuexin,Laishram, Ronibala Devi,Chen, Jingchao,Li, Kangkui,Zhang, Keyang,Zeng, Guangzhi,Fan, Baomin
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supporting information
p. 3991 - 3997
(2019/08/02)
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- Pd(OAc)2-Catalyzed Asymmetric Hydrogenation of α-Iminoesters
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An efficient Pd(OAc)2-catalyzed asymmetric hydrogenation of α-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)2, a less expensive Pd salt with low toxicity, was found to be the most suitable catalyst precursor rather than Pd(TFA)2 which is usually the catalyst of choice for homogeneous asymmetric hydrogenation. The chiral α-arylglycine fragments are widely found in many chiral products and bioactive molecules.
- Chen, Jianzhong,Li, Feilong,Wang, Fang,Hu, Yawen,Zhang, Zhenfeng,Zhao, Min,Zhang, Wanbin
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supporting information
p. 9060 - 9065
(2019/11/19)
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- Enantioselective Iridium-Catalyzed Hydrogenation of α-Keto Amides to α-Hydroxy Amides
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A highly enantioselective iridium-catalyzed hydrogenation of α-keto amides to form α-hydroxy amides has been achieved with excellent results (up to >99% conversion and up to >99% ee, TON up to 100?000). As an example, this protocol was applied to the synthesis of (S)-4-(2-amino-1-hydroxyethyl)benzene-1,2-diol, the enantiomer of norepinephrine, which is widely used as an injectable drug for the treatment of critically low blood pressure. Density functional theory (DFT) calculations were also carried out to reveal the reaction mechanism.
- Gu, Guoxian,Yang, Tilong,Yu, Ouran,Qian, Hua,Wang, Jiang,Wen, Jialin,Dang, Li,Zhang, Xumu
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supporting information
p. 5920 - 5923
(2017/11/10)
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- A method for synthesis of α - keto ester
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A synthetic method of [alpha]-keto ester. The invention relates to the technical field of chemical synthesis. The synthetic method comprises a step of in a solvent, with benzene seleninic acid as a catalyst and air as an oxidizing agent, oxidizing [alpha]-hydroxy acid ester to obtain an oxidized product [alpha]-keto ester. In the method, air is employed as the oxidizing agent, which is clean, is easy to obtain, and is harmless to environment. The method employs the benzene seleninic acid as the catalyst instead of a metal catalyst, so that the [alpha]-keto ester is metabolizable in human body and is ecological friendly since selenium is required microelement of living bodies. The synthetic method is carried out under mild conditions and is less in damage on devices. A system for the method is durable, so that the method is suitable for industrial production.
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Paragraph 0036-0038
(2017/08/25)
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- I 2 /TBHP-Promoted Approach to α-Keto Esters from Trifluoromethyl β-Diketones and Alcohols via C-C Bond Cleavage
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A metal-free oxidative coupling reaction of trifluoromethyl β-diketones with alcohols for the synthesis of α-keto esters in good to excellent yields has been developed. Preliminary mechanistic studies suggest that an I 2 /TBHP promoted sequential iodination, C-C bond cleavage, C-O bond formation and oxidation pathway is involved in this reaction.
- Shao, Tongle,Fang, Xiang,Zhou, Jun,Jin, Chen,Yang, Xueyan,Wu, Fanhong
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supporting information
p. 2018 - 2023
(2017/09/13)
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- Synthesis and evaluation of essential oil-derived β-methoxyacrylate derivatives as high potential fungicides
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Essential oils (EOs) are plant-derived aroma compounds with a wide range of biological activity, but their actions are slow, and they are typically unstable to light or heat, difficult to extract and so on. To find highly potential fungicides derived from natural EOs, a series of essential oil-based β-methoxyacrylate derivatives have been designed and synthesized. The target compounds have been screened for their potential fungicidal activity against eleven species of plant pathogen fungi, including Alternaria alternata, Phomopsis adianticola, Pestalotiopsis theae, Sclerotinia sclerotiorum, etc. Compared with intermediates I, the parent essential oils and azoxystrobin, almost all of essential oil-based β-methoxyacrylate derivatives exhibited significantly better fungicidal activity. Further investigation revealed that some compounds showed remarkable inhibitory activities against Pestalotiopsis theae, Phomopsis adianticola, Sclerotinia sclerotiorum and Magnapothe grisea at different concentrations in contrast to the commercial product azoxystrobin. Compound II-8 exhibited particularly significant fungicidal activity.
- Su, Haihuan,Wang, Wenda,Bao, Longzhu,Wang, Shuangshuang,Cao, Xiufang
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- Synthesis and biological evaluation of kresoxim-methyl analogues as novel inhibitors of hypoxia-inducible factor (HIF)-1 accumulation in cancer cells
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We designed and synthesized strobilurin analogues as hypoxia-inducible factor (HIF) inhibitors based on the molecular structure of kresoxim-methyl. Biological evaluation in human colorectal cancer HCT116 cells showed that most of the synthesized kresoxim-methyl analogues possessed moderate to potent inhibitory activity against hypoxia-induced HIF-1 transcriptional activation. Three candidates, compounds 11b, 11c, and 11d were identified as potent inhibitors against HIF-1 activation with IC50 values of 0.60–0.94?μM. Under hypoxic condition, compounds 11b, 11c, and 11d increased the intracellular oxygen contents, thereby attenuating the hypoxia-induced accumulation of HIF-1α protein.
- Lee, Sanghyuck,Kwon, Oh Seok,Lee, Chang-Soo,Won, Misun,Ban, Hyun Seung,Ra, Choon Sup
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p. 3026 - 3029
(2017/05/31)
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- Rh-catalyzed asymmetric hydrogenation of racemic aldimines via dynamic kinetic resolution
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Catalyzed by a rhodium complex of P-stereogenic diphosphine ligand trichickenfootphos (TCFP), asymmetric hydrogenation of racemic aldimines via dynamic kinetic resolution has been realized for the preparation of chiral arylglycines with good yields and enantioselectivities.
- Fan, Dongyang,Lu, Jian,Liu, Yang,Zhang, Zhenfeng,Liu, Yangang,Zhang, Wanbin
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p. 5541 - 5547
(2016/08/05)
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- Synthesis and fungicidal activity of (E)-α-(Methoxyimino)benzeneacetate derivatives containing 1,2,4-triazole schiff base side Chain
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Figure presented To find new strobilurin analogs with high activity against resistant pathogens, twelve (E)-α-(methoxyimino)benzeneacetate derivatives containing 1,2,4-triazole Schiff base side chain 3a-3l were designed and synthesized. Their structures were confirmed by IR, 1H-NMR, EIMS, and elemental analyses. Bioassays indicated that most of the target compounds showed moderate to good fungicidal activities against Physalospora piricola Nose and Alternaria solani. For example, compounds 3d, 3e, and 3f possessed 99.5%, 100%, and 95.6% inhibition against Physalospora piricola Nose, whereas compounds 3d, 3f, and 3g exhibited 92%, 91%, and 92% inhibition against Alternaria solani at the concentration of 50 mg/L, respectively.
- Song, Hong-Xing,Shi, De-Qing
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p. 1345 - 1348
(2015/04/27)
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- Direct asymmetric hydrogenation of α-keto acids by using the highly efficient chiral spiro iridium catalysts
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A new efficient and highly enantioselective direct asymmetric hydrogenation of α-keto acids employing the Ir/SpiroPAP catalyst under mild reaction conditions has been developed. This method might be feasible for the preparation of a series of chiral α-hydroxy acids on a large scale.
- Yan, Pu-Cha,Xie, Jian-Hua,Zhang, Xiang-Dong,Chen, Kang,Li, Yuan-Qiang,Zhou, Qi-Lin,Che, Da-Qing
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supporting information
p. 15987 - 15990
(2015/02/19)
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- Electrochemical synthesis of the aryl α-ketoesters from acetophenones mediated by Ki
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Two C-O bonds formed in one step: The oxidative coupling reaction of acetophenones with alcohol was developed by a dioxygen activation to afford α-ketoesters under electrochemical conditions. This novel transformation not only provides a simple and efficient approach to synthetize α-ketoester derivatives, but also invents a new strategy to construct a C-O bond by virtue of an anode oxidation (see scheme). Copyright
- Zhang, Zhenlei,Su, Jihu,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 17711 - 17714
(2014/01/17)
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- AN IMPROVED PROCESS FOR THE SYNTHESIS OF STROBILURIN FUNGICIDES VIZ TRIFLOXYSTROBIN AND KRESOXIM-METHYL
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The present invention relates to an improved process for the synthesis of E-isomer of compound of formula (5). It further relates to the conversion of formula (5), wherein R is H, to Intermediate (I) and subsequently to substantially pure Trifloxystrobin, compound of formula (I) in good yield.
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Page/Page column 28; 30
(2013/10/21)
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- METHOXYIMINO COMPOUNDS AND FUNGICIDE COMPOSITION COMPRISING SAME
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The present invention provides a methoxyimino compound, and a fungicide composition comprising same as an active ingredient. The methoxyimino compound of the present invention, which has an excellent antifungal activity against a wide spectrum of fungi even at a low application rate, can be used to protect various crops.
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Page/Page column 15
(2009/07/17)
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- Asymmetric addition of dimethylzinc to α-ketoesters catalyzed by (-)-MITH
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(Chemical Equation Presented) This investigation describes the catalytic asymmetric addition of dimethylzinc to α-ketoesters in the presence of (-)-MITH (5) and triethyl borate as an additive to give the corresponding chiral α-hydroxy esters with good yie
- Wu, Hsyueh-Liang,Wu, Ping-Yu,Shen, Ying-Ying,Uang, Biing-Jiun
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p. 6445 - 6447
(2008/12/22)
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- Facile synthesis of aryl α-keto esters via the reaction of aryl diazoacetate with H2O and DEAD
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A facile synthesis of aryl aα-keto esters in high yields is reported involving the reaction of aryl diazoacetate with H2O and diethyl azodicarboxylate (DEAD) catalyzed by dirhodium acetate. Georg Thieme Verlag Stuttgart.
- Guo, Zhenqiu,Huang, Haoxi,Fu, Qingquan,Hu, Wenhao
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p. 2486 - 2488
(2008/02/11)
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- Fungicidal compounds having a fluorovinyl-or fluoropropenyl-oxyphenyloxime moiety and process for the preparation thereof
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A fungicidal compound of formula (I) having a fluorovinye- or fluoropropenyl-oxyphenyloxime moiety and stereoisomers thereof are useful for protecting crops from fungal diseases: wherein, X is CH or N; Y is O or NH; R1is hydrogen, C1-4alkyl, or halogen-substituted C1-4alkyl, R2is a phenyl group optionally carrying one or more substituents selected from the group consisting of C1-4alkyl, C1-4alkoxy, methylenedioxy and halogen; or a naphthyl group; and R3is hydrogen or CF3.
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- Fungicidial compounds having a fluorovinyloxphyenyl moiety and process for the preparation thereof
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A fungicidal compound of formula (I) having a fluorovinyloxyphenyl moiety and stereoisomers thereof are useful for protecting crops from fungal diseases: wherein: X is CH or N; Y is O or S; Z is O or NH; R1is hydrogen or CF3; and R2is hydrogen, a C1-10alkyl, naphthyl, thiophenyl or a phenyl group optionally carrying one or more substituents selected from the group consisting of C1-6alkyl, halogen-substituted C1-6alkyl, C1-6alkoxy, phenoxy, halogen, and methylenedioxy radicals.
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- Acrylate fungicides
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Compounds of formula I STR1 wherein X is oxygen or sulphur, W is CH or N, m is 0 or 1, and either a) n is 1 and Q is a non-aromatic heterocyclic ring of 3 to 10 ring atoms, containing one to three hetero atoms selected from oxygen, sulphur and nitrogen, which may be substituted and may be fused to another ring, with the proviso a) that if Q is thiazol-2-in-2-yl, it is substituted but not by methylene, and b) Q is not a six membered ring containing only two nitrogen atoms, or b) n is 0 or 1 and STR2 where R1 is alkyl, alkoxy or alkylthio, and R2 is heteroaryl, non aromatic heterocyclyl, optionally substituted cycloalkyl or optionally substituted alkyl containing at least 5 carbon atoms, phenyl substituted by one or more groups selected from halogen, optionally substituted alkyl, alkoxy, haloalkoxy, aryloxy, alkylthio and alkoxycarbonyl, and when R1 is alkyl or alkoxy, or, when W is nitrogen, R2 can also be unsubstituted phenyl, have pesticidal especially fungicidal activity.
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- Acrylate fungicides
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The invention provides compounds of formula I STR1 wherein W, D, R1, R2, R3, x, m, n and p are as defined in the description. The compound have valuable pesticidal activity especially against fungi, insects, nematodes, aca
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- α-arylacrylates and fungicides containing these compounds
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α-Arylacrylates of the general formula I STR1 where Y is substituted or unsubstituted, alkenylene, alkynylene, O,S(O)m, N, oxycarbonyl, carbonyloxy, oxycarbonylalkylene, carbonyloxyalkylene, oxyalkyleneoxy, oxyalkylene, alkyleneoxy, thioalkylen
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- Syntheses of Aryl Glyoxylate. I. The Reaction of Alkyl Dichloro(alkoxy)acetates with Aromatics in the Presence of Lewis Acid
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Ethyl dichloro(ethoxy)acetate(1) and methyl dichloro(methoxy)acetate(2) were characterized.The reaction of 1 and 2 with aromatics in the presence of AlCl3 gave a considerable yield of aromatic α-keto ester.The aromatics included mono- and polymethylbenzene and anisol.The reaction was studied under various conditions and the results were compared with the acylation by ethoxalyl or methoxalyl chloride.The reaction mechanism was also discussed.
- Itoh, Osamu,Nagata, Takayoshi,Nomura, Isamu,Takanaga, Tetsuya,Sugita, Toshio,Ichikawa, Katsuhiko
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p. 810 - 814
(2007/10/02)
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- HALIDE-DIRECTED NITRILE HYDROLYSYS
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Sodium bromide is an effective catalyst for promoting the hydrolysis of aroyl cyanides such that loss of the cyano group is greatly minimized.
- Photis, James M.
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p. 3539 - 3540
(2007/10/02)
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