- Chiral 4 and 5 - disubstituted pyrrolidine -2 - ketone compound as well as preparation method and application thereof
-
The invention belongs to the technical field of organic synthesis, and particularly relates to chiral 4, 5 - disubstituted pyrrolidine -2 - ketone compounds as well as a preparation method and application thereof. The invention firstly uses nitro substituted alkyl (I) and trans α, β - unsaturated 3 - methyl -4 - nitroisoxazole (II) as raw materials, and the asymmetric Michael addition reaction of chiral superbase catalysis I and II is a key step and is hydrolyzed. Esterification and reduction closes the ring, synthesizing a chiral 3, 4 - disubstituted pyrrolidine -2 - ketone compound, including optically pure fenoxone. The asymmetric Michael addition reaction of chiral superbase catalyst for catalyzing 2 -substituted nitroethane (I) and trans α, β -unsaturated 3 - methyl -4 - nitroisoxazole (II) is used for preparing chiral 4 and 5 -disubstituted pyrroli -2 - ketone, and a strapdown is provided for synthesizing chiral 4 and 5 - disubstituted pyrrolidine -2 - ketone skeleton.
- -
-
Paragraph 0055-0059
(2021/11/26)
-
- NHC-Catalyzed Dual Stetter Reaction: A Mild Cascade Annulation for the Syntheses of Naphthoquinones, Isoflavanones, and Sugar-Based Chiral Analogues
-
The N-heterocycle carbene (NHC)-catalyzed dual Stetter cascade reaction is discovered through coupling of β-nitrostyrene with phthalaldehyde under mild conditions to furnish valuable aryl-naphthoquinones. The generality of the new reaction is validated through the development of a C-C and O-C bond forming Stetter cascade reaction using salicylaldehydes to obtain functionalized dihydroisoflavanones. The mild NHC organocatalysis is successfully employed for the construction of optically pure sugar-based naphthoquinones and dihydroisoflavanones. Herein, NHC is found as a unique and powerful organocatalyst to construct homoatomic C-C cross-coupling, heteroatomic O-C bond formation, and cascade cyclization utilizing NO2 as a leaving group at ambient temperature. A mechanistic pathway of the new metal-free catalysis is predicted on the basis of our ESI-MS study of the ongoing reaction and literature.
- Mitra, Rajendra N.,Show, Krishanu,Barman, Debabrata,Sarkar, Satinath,Maiti, Dilip K.
-
-
- Comprehensive evaluation of antioxidant effects of Japanese Kampo medicines led to identification of Tsudosan formulation as a potent antioxidant agent
-
Oxidative stress due to the overproduction of reactive oxygen species plays an important role in the pathogenesis of various diseases. In the present study, we comprehensively evaluated the antioxidant activities of 147 oral formulations of Japanese traditional herbal medicines (Kampo medicines), representing the entire panel of oral Kampo medicines listed in the Japanese National Health Insurance Drug List, using in vitro radical scavenging assays, including the 2,2-diphenyl-1-picrylhydrazyl free radical scavenging activity assay, the superoxide anion scavenging activity assay, and the oxygen radical absorption capacity assay. Three of the formulations tested, namely, Tsudosan, Daisaikoto, and Masiningan, showed the most potent in vitro antioxidant activities and were selected for further investigation of their intracellular and in vivo antioxidant effects. The results of the 2′,7′-dichlorodihydrofluorescin diacetate assay demonstrated that all three Kampo medicines significantly inhibited hydrogen peroxide-induced oxidative stress in human hepatocellular liver carcinoma HepG2 cells. In addition, Tsudosan significantly increased the serum biological antioxidant potential values when orally administrated to mice, indicating that it also had in vivo antioxidant activity. The potent antioxidant activity of Tsudosan may be one of the mechanisms closely correlated to its clinical usage against blood stasis.
- Sato, Naoko,Li, Wei,Takemoto, Hiroaki,Takeuchi, Mio,Nakamura, Ai,Tokura, Emi,Akahane, Chie,Ueno, Kanako,Komatsu, Kana,Kuriyama, Noriko,Onoda, Toshihisa,Higai, Koji,Koike, Kazuo
-
p. 163 - 172
(2018/11/06)
-
- Facile Synthesis of 1,3,5-Triarylbenzenes and 4-Aryl-NH-1,2,3-Triazoles Using Mesoporous Pd-MCM-41 as Reusable Catalyst
-
We report mesoporous nano-Pd-MCM-41 catalyzed rapid and efficient synthesis of 1,3,5-triarylbenzenes via de-nitrative cyclotrimerization of β-nitrostyrenes. All the reactions were very fast and high yielding. The Pd-MCM-41 was also very effective in catalyzing de-nitrative [3+2] cycloaddition of β-nitrostyrenes with TMSN3 to synthesize 4-aryl-NH-1,2,3-triazoles. The catalyst was reused at least up to eight times with minimum loss of catalytic activity.
- Saha, Arijit,Wu, Chia-Ming,Peng, Rui,Koodali, Ranjit,Banerjee, Subhash
-
p. 104 - 111
(2019/01/04)
-
- Cinnamic acid derivative and preparation method and application thereof
-
The invention provides a cinnamic acid derivative. The cinnamic acid derivative is of the structure as shown in the formula I. The invention also provides two methods for preparing the cinnamic acid derivative. The two methods depend on a single bond or double bonds in the structure shown in the formula I. The invention further provides a pesticide. The pesticide comprises the cinnamic acid derivative. In addition, the invention provides a sterilization method. The sterilization method includes the step of applying the cinnamic acid derivative or the pesticide to crops. The crops include rice,wheat, fruit trees and vegetables. The low-toxicity, low-residue-content and high-activity environment-friendly cinnamic acid derivative is developed, and the cinnamic acid derivative pesticide can replace traditional high-toxicity and high-residue-content pesticides.
- -
-
Paragraph 0204; 0205; 0206
(2019/10/22)
-
- Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation
-
ortho-Naphthoquinone-based organocatalysts have been identified as versatile aerobic oxidation catalysts. Primary amines were readily cross-coupled with primary nitroalkanes via deaminative pathway to give nitroalkene derivatives in good to excellent yields. Secondary and tertiary amines were inert to ortho-naphthoquinone catalysts; however, secondary nitroalkanes were readily converted by ortho-naphthoquinone catalysts to the corresponding nitrite species that in situ oxidized the amines to the corresponding N-nitroso compounds. Without using harsh oxidants in a stoichiometric amount, the present catalytic aerobic oxidation protocol utilizes the substrate promiscuity feature to provide a facile access to amine oxidation products under mild reaction conditions.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
-
p. 9216 - 9221
(2019/10/08)
-
- Base-catalyzed reactions enhanced by solid acids: Amine-catalyzed nitroaldol (Henry) reactions enhanced by silica gel or mesoporous silica SBA-15
-
The reactions of various aldehydes with CH3NO2 catalyzed by Et3N, n-C6H13NH2, and Me2N(CH2)2NH2 were accelerated by the addition of silica gel to give aromatic (aliphatic) β-nitroalcohols, aromatic nitroalkenes, and aromatic 1,3-dinitroalkanes, respectively. Mesoporous silica SBA-15 showed higher activity than silica gel for the synthesis of aromatic nitroalkenes by the reactions of the corresponding aldehydes with CH3NO2 catalyzed by n-C6H13NH2.
- Tanemura, Kiyoshi,Suzuki, Tsuneo
-
supporting information
p. 392 - 396
(2017/12/28)
-
- Squaramide-Linked Chloramphenicol Base Hybrid Catalysts for the Asymmetric Michael Addition of 2,3-Dihydrobenzofuran-2-carboxylates to Nitroolefins
-
An array of hybrid catalysts incorporating a chloramphenicol base moiety linked to another chiral scaffold through a squaramide linker were developed and successfully used in the Michael addition of 2,3-dihydrobenzofuran-2-carboxylates to nitroolefins. Control experiments suggested that the hybrid catalysts were more reactive than nonhybridized bifunctional catalysts, and matching of the chirality between the two scaffolds was crucial for high reactivity and stereoselectivity. These hybrid organocatalysts could be used with a variety of substrates. At a 0.5 mol-% catalyst loading, a range of 2,3-dihydrobenzofuran-2-carboxylates derivatives bearing quaternary and tertiary stereogenic centers were obtained in high yields (up to 98 %) with excellent enantioselectivities (up to 99 % ee) and moderate diastereoselectivities (up to 8:92 dr).
- Yan, Linjie,Huang, Guanxin,Wang, Haifeng,Xiong, Fangjun,Peng, Haihui,Chen, Fener
-
supporting information
p. 99 - 103
(2018/01/17)
-
- Method for synthesizing nitroolefin compound
-
The invention relates to a method for synthesizing an organic compound. The method is used for solving the problem of current synthesis of nitroolefin compounds that reaction byproducts are numerous,raw materials are expensive, and some methods are relatively troublesome in aftertreatment. The invention provides a method for preparing a nitroolefin compound. The nitroolefin compound is prepared through subjecting a cinnamyl aldehyde compound, which serves as a starting material, to a reaction with a nitrate and a solvent for 1 to 24 hours at the temperature of 25 DEG C to 150 DEG C. A methodfor direct nitration by using a cheap nitrate is achieved. The method is a new route for synthesizing the nitroolefin compound.
- -
-
Paragraph 0042-0044
(2018/03/26)
-
- Catalyst-free sulfa-Michael addition of pyrimidine-2-thiol to nitroolefins
-
Catalyst-free sulfa-Michael addition of pyrimidine-2-thiol to nitroolefins is described. A series of 2-((2-nitro-1-arylethyl)thio)pyrimidines were efficiently synthesized. The protocol has advantages of wide range of substituents tolerance, no catalyst, additives and bases, mild condition, and high yield. The method can also extend to gram scale.
- Li, Zheng,Song, Geyang,He, Jiaojiao,Du, Yan,Yang, Jingya
-
p. 686 - 698
(2017/09/06)
-
- Benzo-hexatomic ring derivative used as DPP-4 inhibitor and application of benzo-hexatomic ring derivative
-
The invention relates to a benzo-hexatomic ring derivative used as a DPP-4 inhibitor and application of the benzo-hexatomic ring derivative, in particular to compounds shown as in formula I, medicine compositions with the compounds shown as in the formula I and application of the compounds in preparing medicines for treating diseases related to DPP-4 or inhibiting the DPP-4.
- -
-
Paragraph 0469; 0470; 0471
(2016/10/09)
-
- An Asymmetric Vinylogous Michael Cascade of Silyl Glyoximide, Vinyl Grignard, and Nitroalkenes via Long Range Stereoinduction
-
A diastereoselective auxiliary-mediated vinylation/[1,2]-Brook rearrangement/vinylogous Michael cascade of silyl glyoximide, vinylmagnesium bromide, and nitroalkenes is described. The reaction occurs with complete regio- and diastereocontrol in good yield. The diastereoselectivity is induced by a rare instance of 1,7-chirality transfer that is hypothesized to arise from a trans-multihetero-decalin transition state. (Chemical Equation).
- Boyce, Gregory R.,Johnson, Jeffrey S.
-
p. 1712 - 1717
(2016/03/01)
-
- Yolk-shell-structured mesoporous silica: A bifunctional catalyst for nitroaldol-Michael one-pot cascade reaction
-
Great interest in heterogeneous asymmetric catalysis has focused on obtaining an enantioselective cascade reaction through a controllable active site-isolated heterogeneous catalyst. Herein, we utilize a yolk-shell-structured mesoporous silica and assemble an active site-isolated bifunctional heterogeneous catalyst, where chiral cinchonine-based squaramide molecules are anchored within a silicate channel as an outer shell while amine-functionalities are entrapped onto a silicate yolk as an inner core. Structural analyses and characterizations of the heterogeneous catalyst reveal its well-defined single-site chiral active species within its silicate network. Electron microscopy confirms the yolk-shell-structured mesoporous material. As presented in this study, as a bifunctional heterogeneous catalyst, it enables an efficiently nitroaldol-Michael cascade reaction to conduct the three-component coupling of nitromethane, aldehyde and acetylacetone into various chiral diones with high yields and up to 99% enantioselectivities in a one-pot process. As expected, this active site-isolated catalyst not only enhances the catalytic selectivity of the first-step nitroaldol condensation, but also keeps the enantioselectivity of the second-step Michael addition. Moreover, the heterogeneous catalyst can be also recovered easily and recycled repeatedly, making it an interesting feature in a three-component organic transformation.
- An, Juzeng,Cheng, Tanyu,Xiong, Xi,Wu, Liang,Han, Bin,Liu, Guohua
-
p. 5714 - 5720
(2016/07/21)
-
- Palladium(II)-catalyzed C-C and C-O bond formation for the synthesis of C1-benzoyl isoquinolines from isoquinoline: N -oxides and nitroalkenes
-
C1-Benzoyl isoquinolines can be generated via a palladium(ii)-catalyzed C-C and C-O coupling of isoquinoline N-oxides with aromatic nitroalkenes. The reaction proceeds through remote C-H bond activation and subsequent intramolecular oxygen atom transfer (OAT). In this reaction, the N-O bond was designed as a directing group in the C-H bond activation as well as the source of an oxygen atom.
- Li, Jiu-Ling,Li, Wei-Ze,Wang, Ying-Chun,Ren, Qiu,Wang, Heng-Shan,Pan, Ying-Ming
-
supporting information
p. 10028 - 10031
(2016/08/15)
-
- Zeolite Y-assisted nitration of aromatic and heterocyclic compounds and decarboxylative nitration of α,β-unsaturated acids under non-conventional conditions
-
Zeolite Y was found to be an efficient catalyst for a facile nitration of aromatic compounds with acetonitrile as the solvent in the presence of small amounts of HNO3 at room temperature. The reactions afforded mono-nitro derivatives of aromatic compounds in about three hours under stirred conditions with high yields and regioselectivity. The reaction times drastically reduced to about 20 min under sonication and to about 20 s under microwave irradiation. Zeolite is recovered after completion of the reaction and recycled for three to four times without any problem. The approach is particularly appropriate for the conversion of unsaturated cinnamic acids into nitrostyrenes.
- Sudhakar Chary,Rajanna,Krishnaiah,Srinivas
-
p. 1430 - 1434
(2016/03/08)
-
- METHODS AND COMPOSITIONS FOR SELECTIVE AND TARGETED CANCER THERAPY
-
Provided herein are methods and compositions for selective and targeted cancer therapy, in particular certain benzothiophenes, benzothiazoles, oxalamides, N-acyl ureas and chromones, and their use in selectively treating certain adenocarcinomas. In some embodiments, the selective toxicity of the compounds may be mediated through SCD1 and/or CYP450 such as CYP4F11.
- -
-
Page/Page column 227
(2015/03/28)
-
- (1R,2R)-(+)-(1,2)-DPEN-Bonded Sulfonic Acid Resin: A Trifunctional Heterogeneous Catalyst for Asymmetric Michael Additions of Acetone to Nitroolefins
-
Based on (1R,2R)-(+)-(1,2)-DPEN skeleton, a series of primary amine-sulfamide bifunctional catalysts were synthesized, which exhibited excellent catalytic performance in the Michael addition of acetone to β-nitrostyrene. Therefore, a trifunctional heterogeneous catalyst was designed and prepared by simple N-sulfonyl reaction of (1R,2R)-(+)-(1,2)-DPEN and sulfonyl chloride resin. It was employed for the aforementioned addition without any additive and satisfactory results (80.5% conversion; 84.3% ee) were obtained. Meanwhile, the structural and textural properties of the catalyst were characterized by infrared spectroscopy (FT-IR), elemental analysis, SEM, and N2 adsorption and desorption experiments. Finally, the generality of the catalyst was investigated.
- Zhang, Chao,Li, Jing,Tian, Jun,Fang, Wangwang,Li, Yang,Chen, Ligong,Yan, Xilong
-
supporting information
p. 1248 - 1258
(2015/03/30)
-
- Ultrasonically Assisted Rate Enhancements in Trichloroisocyanuric Acid/DMF/NaNO2 Triggered Nitration of Aromatic Compounds and Decarboxylative Nitration of α,β-Unsaturated Acids
-
An efficient and safe method for nitration of aromatic compounds and decarboxylative nitration of α,β-unsaturated acids was developed using trichloroisocyanuric acid (TCICA)/dimethylformamide (DMF) in the presence of NaNO2. The reaction times of conventional protocol reduced from 8-10 h to 1.0-1.5 h (60-90 min) under sonication, even though the yields are comparable under both the conditions.
- Kumar, Mukka Satish,Rajanna, Kamatala Chinna,Venkateswarlu, Marri,Venkanna, Purugula,Saiprakash, Pondichery Kuppuswamy
-
p. 2251 - 2258
(2015/09/22)
-
- 17a-HYDROXYLASE/C17,20-LYASE INHIBITORS
-
The present invention provides compounds of Formula (I), or a pharmaceutically acceptable salt thereof, where R1, R2, R3, R4, R5, R6, A and n are as defined herein. A deuteriated derivative of the compound of Formula (I) is also provided.
- -
-
Paragraph 0331
(2014/03/21)
-
- Highly efficient iridium-catalyzed asymmetric hydrogenation of β-acylamino nitroolefins
-
The first highly efficient Ir-catalyzed enantioselective hydrogenation of β-acylamino nitroolefins is reported. This reaction provides straightforward access to chiral β-amino nitroalkanes in high yields and excellent enantioselectivities (up to >99.9% ee) catalyzed by an Ir-(R,R)-f-spiroPhos complex. This journal is
- Yan, Qiaozhi,Liu, Man,Kong, Duanyang,Zi, Guofu,Hou, Guohua
-
supporting information
p. 12870 - 12872
(2014/12/11)
-
- Unusual reactivity of nitronates with an aryl alkyl carbonate: Synthesis of α-amino esters
-
The monoanions of nitroalkanes are ambident nucleophiles that react with carbonate electrophiles through the oxygen atom. Products arising from reactivity at the carbon atom will yield α-nitro esters, which are precursors for α-amino esters. We demonstrate this in the reactions of nitroalkanes with benzyl phenyl carbonate and DABCO where α-nitro esters are obtained instead of nitrile oxides. The products are readily reduced to α-amino esters. This pathway could be a safe alternative to the Strecker reaction.
- Reddy, Golipalli Ramana,Mukherjee, Debopreeti,Chittoory, Arjun Kumar,Rajaram, Sridhar
-
supporting information
p. 5874 - 5877
(2015/01/08)
-
- A branched domino reaction: Asymmetric organocatalytic two-component four-step synthesis of polyfunctionalized cyclohexene derivatives
-
Take two: By employing two equivalents of an aldehyde in an asymmetric organocatalytic domino reaction, the nucleophilic enamine intermediate is also converted into the corresponding iminium species through oxidation with o-iodoxybenzoic acid. Thus, polyfunctionalized cyclohexene derivatives are formed from two simple starting materials in good yields and stereoselectivities (see scheme; Bn=benzyl, EWG=electron-withdrawing group). Copyright
- Zeng, Xiaofei,Ni, Qijian,Raabe, Gerhard,Enders, Dieter
-
supporting information
p. 2977 - 2980
(2013/04/11)
-
- Ultrasonic and microwave-assisted synthesis of β-nitro styrenes and nitro phenols with tertiary butyl nitrite under acid-free conditions
-
Tertiary butyl nitrite (TBN) is an acid-free and safe nitrating agent that provides preferentially β-nitrostyrenes with cinnamic acids and corresponding nitro derivatives with phenols in good yields under classical conditions. However, ultrasonic and microwave-assisted reactions reduced the reaction times substantially and enhanced the yields from good to excellent. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
- Kumar, M. Satish,Rajanna,Reddy, K. Rajendar,Venkateswarlu,Venkanna
-
supporting information
p. 2672 - 2677
(2013/07/26)
-
- Oxalylchloride/DMF as an efficient reagent for nitration of aromatic compounds and nitro decarboxylation of cinnamic acids in presence of KNO 3 or NaNO2 under conventional and nonconventional conditions
-
Nitration of aromatic compounds and cinnamic acids with oxalylchloride/DMF afforded the corresponding nitro derivatives in the presence of KNO3 or NaNO2 under conventional and nonconventional (ultrasonic and microwave) conditions. The present methodology offers several benefits such as excellent yields, simple work-up procedure, and short reaction times. The yields obtained under present methodology are comparable with those obtained from (POCl3/DMF/KNO3 or NaNO2) and (SOCl 2/DMF/KNO3 or NaNO2) systems followed by shorter reaction times. The reaction times of sonication and microwave conditions are very shorter than those of the conventional conditions.
- Kumar, M. Satish,Reddy, K. Rajendar,Rajanna,Venkanna,Krishnaiah
-
p. 977 - 983
(2013/06/05)
-
- 17α-HYDROXYLASE/C17,20-LYASE INHIBITORS
-
The present invention provides compounds of Formula (I), or a pharmaceutically acceptable salt thereof, where R1, R2, R3, R4, R5, R6, A and n are as defined herein. A deuteriated derivative of the compound of Formula (I) is also provided.
- -
-
Page/Page column 57
(2012/04/04)
-
- One-pot synthesis of nitroalkenes via the Henry reaction over amino-functionalized MIL-101 catalysts
-
Ethylenediamine moieties with different amounts were incorporated into the metal-organic framework MIL-101 to prepare the amino-functionalized MIL-101 materials, which were used as heterogeneous catalysts in the one-pot synthesis of nitroalkenes via the Henry reaction. Various reaction conditions were optimized. Under the optimized conditions, the selectivity towards nitroalkenes is extremely high in combination with nearly complete conversion of the reactant nitroalkanes. The amino-functionalized MIL-101 behaves as a true heterogeneous catalyst, can be easily recovered by filtration, and can be reused at least twice without significant loss of its catalytic performance.
- Yu, Huixian,Xie, Jianwu,Zhong, Yijun,Zhang, Fumin,Zhu, Weidong
-
p. 101 - 104
(2013/01/15)
-
- An efficient, transition-metal-free process for the synthesis of substituted dihydrofurans via a Michael/cyclization tandem reaction
-
An efficient green route for the synthesis of substituted dihydrofurans was developed through a simple base-catalyzed, tandem reaction of nitrostyrene with 1,3-dicarbonyl compounds. The desired products were prepared with a large substrate scope and in excellent yields (up to 95%).
- Wu, Ming-Yu,Wang, Ming-Qi,Li, Kun,Feng, Xing-Wen,He, Ting,Wang, Na,Yu, Xiao-Qi
-
supporting information; experimental part
p. 679 - 683
(2011/03/21)
-
- A novel enzymatic tandem process: Utilization of biocatalytic promiscuity for high stereoselective synthesis of 5-hydroxyimino-4,5-dihydrofurans
-
A lipase-catalyzed protocol for the synthesis of 5-hydroxyimino-4,5- dihydrofurans via tandem coupling between β-nitrostyrenes and 1,3-dicarbonyl compounds was developed in a 'one-pot' strategy. A series of β-nitrostyrenes were employed to expand the scope of this new biocatalytic promiscuity with high stereoselectivity (Z/E up to 99:1) and moderate to good yields. The reaction activity of 1,3-cyclohexanedione was found to be better than linear 2,4-pentanedione, while ethyl acetoacetate and diethylmalonate were not suitable for this reaction under the same conditions. Single-crystal X-ray diffraction analysis indicated that the reaction was stereoselective and Z-stereomer was found to be the major product. A reaction mechanism was supposed to elucidate the biocatalytic process.
- Wu, Ming-Yu,Li, Kun,He, Ting,Feng, Xing-Wen,Wang, Na,Wang, Xiao-Yan,Yu, Xiao-Qi
-
experimental part
p. 2681 - 2688
(2011/04/23)
-
- A novel catalyst-free tandem reaction for the synthesis of 5-hydroxy-1,5-dihydro-2 h -pyrrol-2-ones in water medium
-
A novel catalyst-free, water-medium, tandem reaction for the synthesis of 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones was developed through a one-pot strategy from nitroethylenes and 1,3-dicarbonyl compounds. A series of 1-aryl-2-nitroethenes and 1-nitroalk-1-enes were surveyed to determine the scope of this tandem reaction with moderate to good yield. Georg Thieme Verlag Stuttgart - New York.
- Wu, Ming-Yu,Li, Kun,Wang, Na,He, Ting,Yu, Xiao-Qi
-
experimental part
p. 1831 - 1839
(2011/07/31)
-
