- Dimethyl Sulfoxide Serves as a Dual Synthon: Construction of 5-Methyl Pyrimidine Derivatives via Four Component Oxidative Annulation
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An efficient potassium persulfate mediated four component reaction for the construction of 5-methyl pyrimidine derivatives has been established from readily available methyl ketones, amidine hydrochlorides and dimethyl sulfoxide. This transformation featu
- Xu, Cheng,Jiang, Shi-Fen,Wen, Xiao-Hui,Zhang, Qin,Zhou, Zhi-Wen,Wu, Yan-Dong,Jia, Feng-Cheng,Wu, An-Xin
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- Enantioselective Copper-Catalyzed Electrophilic Sulfenylation of Cyclic Imino Esters
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Herein we report an enantioselective sulfenylation of cyclic imino esters with the efficient and versatile sulfenylation reagent S-alkyl 4-methylbenzenesulfonothioates. By utilizing the Cu/tBu-Phosferrox catalytic system, we can assemble diverse S-alkyl groups into the cyclic imino esters under mild conditions in good yields and with excellent enantioselectivities. Remarkably, this method demonstrates a high tolerance of diverse functional groups and proves to be applicable in the late-stage functionalization of pharmaceuticals.
- Chen, Zhiwei,Lin, Huaxin,Han, Jian,Fang, Dongmei,Wang, Min,Liao, Jian
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supporting information
p. 9146 - 9150
(2021/11/30)
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- Design and synthesis of Mannich base-type derivatives containing imidazole and benzimidazole as lead compounds for drug discovery in Chagas Disease
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The protozoan parasite Trypanosoma cruzi is the causative agent of Chagas disease, the most important parasitic infection in Latin America. The only treatments currently available are nitro-derivative drugs that are characterised by high toxicity and limited efficacy. Therefore, there is an urgent need for more effective, less toxic therapeutic agents. We have previously identified the potential for Mannich base derivatives as novel inhibitors of this parasite. To further explore this family of compounds, we synthesised a panel of 69 new analogues, based on multi-parametric structure-activity relationships, which allowed optimization of both anti-parasitic activity, physicochemical parameters and ADME properties. Additionally, we optimized our in vitro screening approaches against all three developmental forms of the parasite, allowing us to discard the least effective and trypanostatic derivatives at an early stage. We ultimately identified derivative 3c, which demonstrated excellent trypanocidal properties, and a synergistic mode of action against trypomastigotes in combination with the reference drug benznidazole. Both its druggability and low-cost production make this derivative a promising candidate for the preclinical, in vivo assays of the Chagas disease drug-discovery pipeline.
- Atherton, Richard L.,Kelly, John M.,Olmo, Francisco,Sanz-Serrano, Julen,Alcolea, Verónica,Beltran-Hortelano, Iván,Pérez-Silanes, Silvia,Rubio-Hernández, Mercedes
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- Mild Darzens Annulations for the Assembly of Trifluoromethylthiolated (SCF3) Aziridine and Cyclopropane Structures
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We report mild new annulation approaches to trisubstituted trifluoromethylthiolated (SCF3) aziridines and cyclopropanes via Darzens inspired protocols. The products of these anionic annulations, rarely studied previously, possess attractive features rendering them valuable building blocks for synthesis platforms. In this study, trisubstituted acetophenone nucleophiles bearing SCF3 and bromine substituents in their α position were shown to undergo [2 + 1] annulations with vinyl ketones and tosyl-protected imines under mild reaction conditions.
- Delost, Michael D.,Njardarson, Jon T.
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supporting information
p. 6121 - 6125
(2021/08/16)
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- A silver-catalyzed radical ring-opening reaction of cyclopropanols with sulfonyl oxime ethers
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A silver-catalyzed ring-opening reaction of cyclopropanols with sulfonyl oxime ethers has been developed. The protocol was conducted under mild reaction conditions to provide a series of ?-keto oxime ethers with moderate to good yields. The reaction proceeded in a stereoselective manner for CF3-containing oxime ethers to provide a single stereoisomer, while an inseparableEandZmixture was obtained for CN-containing oxime ethers. Mechanistic studies indicate that the reaction proceededviaa radical mechanism.
- Wang, Xin,Zeng, Xiaobao,Zhang, Yanan,Zhao, Yu,Zhu, Li
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supporting information
p. 3734 - 3739
(2020/06/03)
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- Palladium-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted: O-carboranes containing α,β-unsaturated carbonyls
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With the help of a carboxylic acid directing group, Pd-catalyzed regioselective synthesis of B(4,5)-or B(4)-substituted o-carboranes containing α,β-unsaturated carbonyls has been reported. The-COOH, removed during the course of the reaction, is responsible for controlling the regioselectivity. The desired products could be obtained in moderate to good yields.
- Li, Jiaoyi,Lu, Jian,Tian, Song,Wang, Qian,Zhang, Chuyi,Zhang, Jianwei,Zhou, Ling
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p. 4723 - 4727
(2020/07/13)
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- PROCESS FOR THE DIRECT ALPHA-METHYLENATION OF KETONES
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The invention relates to a process for preparing an α-methylene ketone comprising the step of reacting a ketone with formaldehyde in the presence of a catalyst which is an organic compound comprising at least one acid function or the corresponding salt, ester or amide thereof and at least one amine function or the corresponding ammonium salt, or a zwitterion thereof.
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Page/Page column 16; 17
(2020/06/10)
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- Asymmetric "clip-Cycle" Synthesis of Pyrrolidines and Spiropyrrolidines
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The development of an asymmetric "clip-cycle"synthesis of 2,2- and 3,3-disubstituted pyrrolidines and spiropyrrolidines, which are increasingly important scaffolds in drug discovery programs, is reported. Cbz-protected bis-homoallylic amines were activate
- Maddocks, Christopher J.,Ermanis, Kristaps,Clarke, Paul A.
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supporting information
p. 8116 - 8121
(2020/11/02)
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- Copper-Catalyzed Asymmetric Hydrosilylation of β-Nitroethyl Aryl Ketones
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A copper-catalyzed asymmetric hydrosilylation of β-nitroethyl aryl ketones has been disclosed, and the corresponding chiral alcohols could be obtained in high yields (up to 99% yield) and excellent enantioselectivities (up to 96% ee). Moreover, the reaction worked well on a gram scale with 0.3 mol % of ligand loading, indicating that our protocol has potential applications in the synthesis of important pharmaceuticals such as Tranylcypromine and Ticagrelor.
- Zeng, Weijun,Tan, Xuefeng,Yu, Yang,Chen, Gen-Qiang,Zhang, Xumu
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supporting information
p. 858 - 862
(2020/01/31)
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- Synthesis of novel multi-functionalized pyrrolidines by [3 + 2] dipolar cycloaddition of azomethine ylides and vinyl ketones
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Abstract: An efficient and easy synthetic route to substituted pyrrolidine derivatives has been established through [3 + 2] dipolar cycloaddition of vinyl ketones and azomethine ylides. The reactions proceed smoothly, under mild conditions, affording mode
- Pe?i?, Marko S.,Bugarinovi?, Jovana P.,Mini?, Aleksandra,Ili? Komatina, Danijela,Pejovi?, Anka,?mit, Biljana,Stevanovi?, Dragana,Damljanovi?, Ivan
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p. 663 - 679
(2019/03/11)
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- Rh-Catalyzed Decarbonylative Addition of Salicylaldehydes with Vinyl Ketones: Synthesis of Taccabulins A–E
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A rhodium-catalyzed decarbonylative addition of salicylaldehydes with vinyl ketones was developed to synthesize o-hydroxydihydrochalcones (2-hydroxyphenethyl ketones). These decarbonylative addition reactions afforded various functionalized o-hydroxydihydrochalcones in moderate to good yields with broad functional group tolerance and selectivity. This method was also applied further in the divergent synthesis of dihydrochalcone derived taccabulins A–E.
- Rao, Maddali L. N.,Ramakrishna, Boddu S.
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p. 7545 - 7554
(2019/12/15)
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- Method for synthesizing alpha,beta-unsaturated aryl ketone compound from dimethyl sulfoxide and arylethanone
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The invention discloses a method for synthesizing an alpha,beta-unsaturated aryl ketone compound from dimethyl sulfoxide and arylethanone. According to the method, dimethyl sulfoxide and arylethanoneare subjected to a one-pot reaction in the presence of carboxylate and persulfate so as to produce the alpha,beta-unsaturated aryl ketone compound. The method uses dimethyl sulfoxide as a methylenation reagent and employs a one-pot process for high-selectivity high-yield synthesis of the alpha,beta-unsaturated aryl ketone compound from arylethanone; and the method is simple to operate, low in cost, friendly to environment and beneficial for industrial production.
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Paragraph 0044; 0045-0050; 0063-0068
(2018/03/24)
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- Method for synthesizing alpha,beta-unsaturated ketone compounds from dimethyl sulfoxide and ketone compounds
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The invention discloses a method for synthesizing alpha,beta-unsaturated ketone compounds from dimethyl sulfoxide and ketone compounds. According to the method, dimethyl sulfoxide and ketone compoundsare subjected to a one-pot reaction in the presence of carboxylate and persulfate so as to produce the alpha,beta-unsaturated ketone compounds. The method uses dimethyl sulfoxide as a methylenation reagent and employs a one-pot process for high-selectivity high-yield synthesis of the alpha,beta-unsaturated ketone compounds from the ketone compounds; and the method is simple to operate, low in cost, friendly to environment and beneficial for industrial production.
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Paragraph 0047-0049; 0068-0071
(2018/03/24)
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- Stereoselective Allylic Alkylation of 1-Pyrroline-5-carboxylic Esters via a Pd/Cu Dual Catalysis
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The asymmetric allylation of 1-pyrroline-5-carboxylic esters has been accomplished through a synergistic Pd/Cu catalyst system under mild reaction conditions. The mechanistic studies suggested that (1) nucleophilic attack is the enantiodiscriminating step; (2) the cooperative action of two chiral reactive species, N-metalated azomethine ylides and ?€-allylpalladium, is most likely responsible for its high reactivity and excellent enantioselectivity (up to >99% ee); and (3) the steric hindrance and electronic factors of the allylic electrophiles and imino ester substrates are crucial for the formation of the linear products. A series of 3,4-2H-pyrrole derivatives bearing a quaternary stereogenic center were easily synthesized in high yields and with high to excellent regioselectivity and enantioselectivity.
- Liu, Penglin,Huo, Xiaohong,Li, Bowen,He, Rui,Zhang, Jiacheng,Wang, Tianhong,Xie, Fang,Zhang, Wanbin
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supporting information
p. 6564 - 6568
(2018/10/20)
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- Enantioselective addition of selenosulfonates to α,β-unsaturated ketones
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An organo-catalyzed enantioselective addition of selenosulfonates to α,β-unsaturated ketones was developed for the first time. With a chiral squaramide as an efficient catalyst, the desired α-selenylated ketones were obtained in a good yields with high enantioselectivity up to 89% ee, and good results could be obtained on a gram scale. The products could also be efficiently transformed into useful building blocks with a propenylic stereocenter; the strategy presented in this study may find further applications in organic synthesis.
- Luo, Shilong,Zhang, Nan,Wang, Zhen,Yan, Hailong
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p. 2893 - 2901
(2018/05/03)
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- Structural Modification of Natural Product Ganomycin i Leading to Discovery of a α-Glucosidase and HMG-CoA Reductase Dual Inhibitor Improving Obesity and Metabolic Dysfunction in Vivo
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It is a great challenge to develop drugs for treatment of metabolic syndrome. With ganomycin I as a leading compound, 14 meroterpene derivatives were synthesized and screened for their α-glucosidase and HMG-CoA reductase inhibitory activities. As a result, a α-glucosidase and HMG-CoA reductase dual inhibitor ((R,E)-5-(4-(tert-butyl)phenyl)-3-(4,8-dimethylnona-3,7-dien-1-yl)furan-2(5H)-one, 7d) with improved chemical stability and long-term safety was obtained. Compound 7d showed multiple and strong in vivo efficacies in reducing weight gain, lowering HbAlc level, and improving insulin resistance and lipid dysfunction in both ob/ob and diet-induced obesity (DIO) mice models. Compound 7d was also found to reduce hepatic steatosis in ob/ob model. 16S rRNA gene sequencing, SCFA, and intestinal mucosal barrier function analysis indicated that gut microbiota plays a central and causative role in mediating the multiple efficacies of 7d. Our results demonstrate that 7d is a promising drug candidate for metabolic syndrome.
- Wang, Kai,Bao, Li,Zhou, Nan,Zhang, Jinjin,Liao, Mingfang,Zheng, Zhongyong,Wang, Yujing,Liu, Chang,Wang, Jun,Wang, Lifeng,Wang, Wenzhao,Liu, Shuangjiang,Liu, Hongwei
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p. 3609 - 3625
(2018/05/01)
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- Indium(III)-Catalyzed Hydration and Hydroalkoxylation of α,β-Unsaturated Ketones in Aqueous Media
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The hydration of α,β-unsaturated ketones with water proceeded efficiently in the presence of In(OTf)3 (20 mol%) in aqueous media to afford synthetically versatile β-hydroxyketones in moderate to good yields with good functional group compatibility. The method also can be extended to the hydroalkoxylation of α,β-unsaturated ketones with various alcohols for the efficient synthesis of β-alkoxyketones as well as tetrahydrofuran derivatives. (Figure presented.).
- Yun, Jin-Jin,Zhi, Man-Ling,Shi, Wen-Xiao,Chu, Xue-Qiang,Shen, Zhi-Liang,Loh, Teck-Peng
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supporting information
p. 2632 - 2637
(2018/05/30)
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- Chromium(III)-Catalyzed Addition of Water and Alcohol to α,β-Unsaturated Ketones for the Synthesis of β-Hydroxyl and β-Alkoxyl Ketones in Aqueous Media
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An efficient chromium(III) chloride-catalyzed Michael-type reaction of water or alcohol with α,β-unsaturated ketones is developed. A variety of α,β-unsaturated ketones effectively reacted with either water or alcohols to give the corresponding β-hydroxyl ketones or β-alkoxyl ketones in modest to high yields with excellent compatibility to various functional groups. The approach was further utilized for the preparation of synthetically useful compounds containing tetrahydrofuran skeleton.
- Yun, Jin-Jin,Liu, Xuan-Yu,Deng, Wei,Chu, Xue-Qiang,Shen, Zhi-Liang,Loh, Teck-Peng
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p. 10898 - 10907
(2018/09/06)
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- Transition Metal-Free α-Csp3-H Methylenation of Ketones to Form C=C Bond Using Dimethyl Sulfoxide as Carbon Source
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A direct α-Csp3-H methylenation of arylketones to form C=C bond using dimethyl sulfoxide as one-carbon source is achieved under transition metal-free reaction condition. Various aryl ketone derivatives react readily with DMSO, producing the α,β-unsaturated carbonyl compounds in yields of 42 to 90%. This method features a transition metal-free reaction condition, wide substrate scope and using DMSO as novel one-carbon source to form C=C bond, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyl compounds. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.
- Liu, Yu-Feng,Ji, Peng-Yi,Xu, Jing-Wen,Hu, Yu-Qun,Liu, Qiang,Luo, Wei-Ping,Guo, Can-Cheng
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p. 7159 - 7164
(2017/07/26)
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- Enantioselective Synthesis of Quaternary Δ4- and Δ5-Dehydroprolines Based on a Two-Step Formal [3+2] Cycloaddition of α-Aryl and α-Alkyl Isocyano(thio)acetates with Vinyl Ketones
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A divergent synthesis of optically active quaternary Δ4- and Δ5-dehydro prolines is developed based on the first catalytic enantioselective conjugate addition of α-substituted isocyano(thio)acetates to vinyl ketones that is general for both α-aryl and α-alkyl isocyano(thio)acetates. The new tetrasubstituted C?N stereocenter is formed without the need of any metal salt due to a bifunctional tertiary amine/squaramide catalyst, featuring a bulky polyaryl sidearm and an unusually short squaramide diamide H???H interatomic distance in the solid state.
- Odriozola, Amaiur,Oiarbide, Mikel,Palomo, Claudio
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supporting information
p. 12758 - 12762
(2017/09/25)
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- β2, 2-Amino Acid N-Carboxyanhydrides Relying on Sequential Enantioselective C(4)-Functionalization of Pyrrolidin-2,3-diones and Regioselective Baeyer–Villiger Oxidation
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A catalytic enantioselective entry to β2, 2-amino acids enabling their direct coupling with nucleophiles is described. The approach is based upon an effective bifunctional Br?nsted base catalyzed construction of a quaternary carbon stereocenter at C4 position of pyrrolidin-2,3-diones. Subsequent regioselective Baeyer–Villiger oxidation of the resultant adducts gives β2, 2-amino acid N-carboxyanhydrides as the reactive species, which can further react with nucleophiles. Following this strategy both, β2, 2-amino acid derivatives with different functionalities at the newly created stereocenter, and spirocyclic structures can be efficiently prepared.
- Badiola, Eider,Olaizola, Iurre,Vázquez, Ana,Vera, Silvia,Mielgo, Antonia,Palomo, Claudio
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supporting information
p. 8185 - 8195
(2017/06/23)
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- Catalytic Asymmetric Synthesis of Quaternary Barbituric Acids
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The catalytic asymmetric α-functionalization of prochiral barbituric acids, a subtype of pseudosymmetric 1,3-diamides, to yield the corresponding 5,5-disubstituted (quaternary) derivatives remains essentially unsolved. In this study 2-alkylthio-4,6-dioxopirimidines are designed as key 1,3-diamide surrogates that perform exceedingly in amine-squaramide catalyzed C-C bond forming reactions with vinyl ketones or Morita-Baylis-Hillmann-type allyl bromides as electrophiles. Mild acid hydrolysis of adducts affords barbituric acid derivatives with an in-ring quaternary carbon in unprecedented enantioselectivity, offering valuable materials for biological evaluations.
- Del Pozo, Sandra,Vera, Silvia,Oiarbide, Mikel,Palomo, Claudio
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supporting information
p. 15308 - 15311
(2017/11/06)
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- Morita-Baylis-Hillman Reaction of α,β-Unsaturated Ketones with Allylic Acetates by the Combination of Transition-Metal Catalysis and Organomediation
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An intermolecular Morita-Baylis-Hillman (MBH) reaction of α,β-unsaturated ketones with allylic acetates under the catalysis of 10 mol % of tetrakis(triphenylphosphine)palladium(0) and mediation of tributylphosphine has been developed in the presence of acetic acid, affording the desired α-coupling products. The MBH reaction has the advantages of good tolerance to many functional groups, excellent regioselectivity and E-stereoselectivity, and moderate to good yields.
- Li, Ya-Qiong,Wang, Hai-Jun,Huang, Zhi-Zhen
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p. 4429 - 4433
(2016/07/06)
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- Direct Synthesis of γ-Keto Sulfones from Allylic Alcohols: One-Pot Palladium(II)-Catalyzed Generation of Enones Followed by Water-Mediated 1,4-Addition of Organosulfinates
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Allylic alcohols were exploited as synthetic precursors of γ-keto sulfones. The reaction involved the one-pot generation of α,β-enones in situ from the allylic alcohols by using a PdII–dioxygen catalytic system and subsequent sulfa-Michael addition in the presence of water. Importantly, water was identified as a sustainable substitute for a toxic copper salt to promote organosulfonyl addition. Diverse examples of aromatic and aliphatic γ-keto sulfones were prepared. Specially, Ar–X (X = Br, Cl) bonds were tolerated, which indicated a chemoselective catalytic system for the preparation of halogen-bearing γ-keto sulfones. This one-pot method does not require an acid, a base, or isolation of any intermediate. Control experiments indicated that the active catalyst of the first step also promoted the subsequent C–S bond-formation reaction. Water was found to accelerate the reaction rate and to be involved in the protonolysis of the σ-alkylpalladium complex, as corroborated by deuterium incorporation.
- Vellakkaran, Mari,Andappan, Murugaiah M. S.,Nagaiah, Kommu,Nanubolu, Jagadeesh Babu
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supporting information
p. 3575 - 3583
(2016/07/28)
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- 1,4-Diazabicyclo[2.2.2]octane-Promoted Aminotrifluoromethylthiolation of α,β-Unsaturated Carbonyl Compounds: N-Trifluoromethylthio-4-nitrophthalimide Acts as Both the Nitrogen and SCF3 Sources
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A novel difunctionalization reaction is described. It uses N-trifluoromethylthio-4-nitrophthalimide as the reagent, which serves as both the nitrogen and SCF3 sources. In the presence of DABCO (1,4-diazabicyclo[2.2.2]octane), the nitrogen and SCF3 groups can be incorporated into α,β-unsaturated carbonyl compounds easily and give versatile β-amino ketones and esters in good yields. This difunctionalization reaction features mild reaction conditions, high atom-economy, and efficient access to α-SCF3 amino acids.
- Xiao, Qing,He, Qijie,Li, Juncheng,Wang, Jun
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supporting information
p. 6090 - 6093
(2016/01/09)
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- N-Heterocyclic carbene-catalyzed double acylation of enones with benzils
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Thiazolium carbene-catalyzed reaction of aromatic 1,2-diketones with enones in aprotic solvents gave double acylation products in good yields, whereas hydroacylation products formed by Stetter reaction were not detected at all. These results suggested the generation of aroyloxyenamine species from the 1,2-diketones instead of hydroxyenamines (Breslow intermediates). This journal is
- Takaki, Ken,Ohno, Akira,Hino, Makoto,Shitaoka, Takashi,Komeyama, Kimihiro,Yoshida, Hiroto
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p. 12285 - 12288
(2014/12/11)
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- Oxa-Michael addition promoted by the aqueous sodium carbonate
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An efficient Michael addition of alcohols to activated alkenes promoted by sodium carbonate with water as reaction medium has been developed. The reaction provides a general, economical and environmentally friendly approach for the synthesis of β-alkoxycarbonyl compounds.
- Guo, Shi-Huan,Xing, Sheng-Zhu,Mao, Shuai,Gao, Ya-Ru,Chen, Wen-Liang,Wang, Yong-Qiang
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supporting information
p. 6718 - 6720
(2014/12/11)
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- Boron-trihalide-promoted regioselective ring-opening reactions of gem-difluorocyclopropyl ketones
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Boron trihalide-promoted ring-opening reactions of gem-difluorocyclopropyl ketones to give the corresponding β-trifluoromethyl ketones and β-halodifluoromethyl ketones were described. It was found that boron trihalides act as both Lewis acids and nucleophiles and the proximal bond prefers to cleave in this transformation.
- Yang, Tang-Po,Li, Qiang,Lin, Jin-Hong,Xiao, Ji-Chang
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supporting information
p. 1077 - 1079
(2014/01/17)
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- Stereoselective access to trisubstituted cyclopentanols from chiral unsaturated oxo esters by ketyl radical cyclization
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Substituted cyclopentanols with three contiguous stereocenters were prepared with impressive diastereocontrol through a samarium diiodide induced 5-exo-trig radical process. The chiral unsaturated oxo ester precursors were prepared with ee values up to 90 % from propionaldehyde through a two-step organocatalyzed aldolization and Wittig-Horner olefination reaction sequence. Copyright
- Feuillastre, Sophie,Pelotier, Beatrice,Piva, Olivier
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supporting information
p. 1753 - 1759
(2014/03/21)
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- Stereoselective Access to Trisubstituted Cyclopentanols from Chiral Unsaturated Oxo Esters by Ketyl Radical Cyclization
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Substituted cyclopentanols with three contiguous stereocenters were prepared with impressive diastereocontrol through a samarium diiodide induced 5-exo-trig radical process. The chiral unsaturated oxo ester precursors were prepared with ee values up to 90 % from propionaldehyde through a two-step organocatalyzed aldolization and Wittig-Horner olefination reaction sequence.
- Feuillastre, Sophie,Pelotier, Béatrice,Piva, Olivier
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supporting information
p. 1753 - 1759
(2015/10/05)
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- Oxygen as single oxidant for two steps: Base-free one-pot Pd(ii)-catalyzed alcohol oxidation & arylation to halogen-intact β-aryl α,β-enones
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Using oxygen as the sole oxidant for two steps, we developed a new method to synthesize β-aryl α,β-enones by fine-tuning the Pd(ii)-catalyzed oxidation of allyl alcohol to subsequent arylation with arylboronic acids, arylboronic ester and aryltrifluoroborate salt. This one-pot green method does not require copper salt, base, and intermediate isolation. Halogen-bearing chalcones, dibenzylideneacetones and arylalkyl enones were synthesized in good yields. This journal is
- Vellakkaran, Mari,Andappan, Murugaiah M. S.,Nagaiah, Kommu
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p. 45490 - 45494
(2014/12/10)
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- Weinreb Amide based building block for convenient access to vinyl ketones
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A new strategy for the synthesis of vinyl ketones has been achieved. Hitherto unknown and easily accessible, β-phenylseleno-N-methoxy-N- methylpropanamide, obtained through two simple reactions, served as a building block for convenient access to vinyl ketones. The N-methoxy-N-methyl amide moiety ensured no overaddition of the Grignard reagent and, hence, the excellent formation of β-phenylseleno ketones; oxidative work-up with hydrogen peroxide provided ready access to the vinyl ketones with concomitant loss of phenylselanol. Georg Thieme Verlag Stuttgart · New York.
- Tiwari, Praveen Kumar,Aidhen, Indrapal Singh
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supporting information
p. 1777 - 1780
(2013/09/12)
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- 2-catalyzed conjugate addition of arylboronic acids to α,β-unsaturated ketones under ligand-free and neutral conditions
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A simple and efficient Ru-catalyzed conjugate addition reaction of arylboronic acids to α,β-unsaturated ketones under neutral conditions without any additional ligands has been developed. This Ru(II)-catalytic system both fulfilled the inhibition of the β-hydride elimination in the catalytic cycle and minimized the protonolysis of arylboronic acids.
- Zhang, Lei,Xie, Xiaomin,Fu, Lei,Zhang, Zhaoguo
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p. 3434 - 3437
(2013/06/26)
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- PROTEIN CROSSLINKING INHIBITOR AND USE OF THE SAME
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The present invention relates to: a ketone compound having transglutaminase-inhibiting activity, which is represented by the following Formula 1, 2, or 3: wherein R1 is a substituted or unsubstituted aryl or heterocyclyl group, R2, R3, and R4 are hydrogen atoms, n is 2, X is halogen, R5 and R6 independently represent a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl, aryl, or aralkyl group, wherein R5 and R6 are not hydrogen atoms at the same time, or R5 and R6 may be taken together to form a saturated or unsaturated and substituted or unsubstituted heterocyclyl group containing a nitrogen atom (N); an inhibitor of protein crosslinking comprising the compound; and a composition for preventing or treating a protein-crosslinking causative disease, which comprises the compound or the protein crosslinking inhibitor.
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Page/Page column 24
(2012/11/08)
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- Tandem ene-reaction/hydroamination of amino-olefin and -allene compounds catalyzed by Bi(OTf)3
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Bi(OTf)3 was proven to act as an effective catalyst for tandem ene-reaction/hydroamination of amino-olefin and amino-allene compounds with some enophiles, giving rise to functionalized N-heterocycles in good yields.
- Komeyama, Kimihiro,Kouya, Yuusuke,Ohama, Yuuki,Takaki, Ken
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supporting information; body text
p. 5031 - 5033
(2011/06/09)
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- Highly efficient route to functionalized tetrahydrocarbazoles using a tandem cross-metathesis/intramolecular-hydroarylation sequence
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The scope of the novel ruthenium-catalyzed tandem cross-metathesis/ intramolecular-hydroarylation sequence is described. This methodology offers a practical and efficient synthesis of structurally diverse and complex tetrahydrocarbazoles in good to excellent yields (up to 98%). Moreover, preliminary efforts towards the development of an enantioselective version of the current process by sequential catalysis with ruthenium complex and chiral amine are presented, with high yields and enantioselectivities (up to 88% yield and 91% ee).
- An, Xiao-Lei,Chen, Jia-Rong,Li, Chang-Feng,Zhang, Fu-Gen,Zou, You-Quan,Guo, Ying-Cen,Xiao, Wen-Jing
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p. 2258 - 2265
(2011/06/11)
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- Synthesis of water-tolerant indium homoenolate in aqueous media and its application in the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chloride
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The first water-tolerant, ketone-type indium homoenolate was synthesized via the oxidative addition of In/InCl3 to enones. The reaction proceeds exclusively in aqueous media. Both indium and indium(III) chloride are necessary for the smooth conversion of the reaction. Similar results were obtained when InCl or InCl2 was used in place of In/InCl3. The synthetic utility of the indium homoenolate was demonstrated through the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling of indium homoenolate with acid chloride.
- Shen, Zhi-Liang,Goh, Kelvin Kau Kiat,Cheong, Hao-Lun,Wong, Colin Hong An,Lai, Yin-Chang,Yang, Yong-Sheng,Loh, Teck-Peng
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supporting information; experimental part
p. 15852 - 15855
(2011/01/10)
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- The first heterogeneous carbonylative Stille coupling of organostannanes with aryl iodides catalyzed by MCM-41-supported bidentate phosphine palladium(0) complex
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The first heterogeneous carbonylative Stille coupling reaction of organostannanes with aryl iodides under an atmospheric pressure of carbon monoxide has been achieved in DMF at 80 °C in the presence of a catalytic amount of an MCM-41-supported bidentate phosphine palladium(0) complex [MCM-41-2P-Pd(0)], yielding a variety of unsymmetrical ketones in good to high yields. This polymeric palladium catalyst exhibited higher activity and selectivity than PdCl2(PPh3)2 and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decrease in activity. Our system not only avoids the use of carbon monoxide under pressure, but also solves the basic problem of palladium catalyst recovery and reuse. The Royal Society of Chemistry 2009.
- Cai, Mingzhong,Zheng, Guomin,Ding, Guodong
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experimental part
p. 1687 - 1693
(2010/06/11)
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- Palladium-catalysed carbonylative cross-coupling reactions of aryl iodides and vinyl boron derivatives as a straightforward route to aryl vinyl ketones
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The carbonylative cross-coupling of potassium vinyl trifluoroborate or 2,4,6-trivinyltricycloboroxane with aryl iodides under mild conditions affords aryl vinyl ketones. The optimisation of the reaction conditions leads to the targeted enones in good yiel
- Pirez, Cyril,Dheur, Julien,Sauthier, Mathieu,Castanet, Yves,Mortreux, André
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experimental part
p. 1745 - 1748
(2009/12/08)
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- The cation exchange resin-promoted coupling of alkynes with aldehydes: one-pot synthesis of α,β-unsaturated ketones
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Alkynes undergo smooth coupling with aldehydes in the presence of Amberlyst-15 at room temperature to produce the corresponding α,β-unsaturated ketones in high yields with E-geometry. The use of an inexpensive, readily available, and recyclable cation exchange resin makes this method quite simple and convenient.
- Yadav,Subba Reddy,Vishnumurthy
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p. 4498 - 4500
(2008/09/21)
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- Copper-catalyzed rearrangement of vinyl oxiranes
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A novel copper-catalyzed vinyl oxirane ring expansion protocol has been developed. A wide range of vinyl oxiranes can be rearranged to 2,5-dihydrofurans in excellent yields in the presence of electrophilic copper(II) acetylacetonate catalysts. Regioisomeric vinyl oxiranes can be converted to a single dihydrofuran product using these conditions. This method uses low catalyst loadings (0.5-5 mol %), has good tolerance of substitution patterns, and can be done in the absence of solvent. Copyright
- Batory, Lindsay A.,McInnis, Christine E.,Njardarson, Jon T.
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p. 16054 - 16055
(2007/10/03)
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- Synthesis of new photoactivatable phenylalanine analogues and their incorporation into a model peptide - Phenylseleno derivatives as precursors of α,β-unsaturated ketones in peptide synthesis
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The asymmetric synthesis of (S)-Boc-p-(propanoyl)phenylalanine (10) was performed by alkylation of sultam N-(di- phenylmethylene)glycinate (4). Different pathways for the introduction of a phenylseleno moiety α to the ketone function were investigated. (S)-Boc-p-[2′-(phenylselenenyl)propanoyl]phenylalanine (11) was easily obtained from (S)-Boc-p-(propanoyl)phenylalanine (10). However, the phenylseleno moiety α to the carbonyl group was found to be unstable to the conditions required for solid-phase peptide synthesis. Therefore, (2S)-Boc-p-[2′-(phenylselenenyl)propanoyl]phenylalanine (11) was transformed into Boc-p-[3′-(phenylselenenyl)propanoyl]phenylalanine (13), which was successfully incorporated into the sequence of a model peptide. The corresponding enone function generated under mild acidic conditions was found to be stable in aqueous solution at pH = 7, but suitably reactive upon irradiation. Thus, these phenylalanine analogs bearing an unsaturated ketone represent new photoreactive probes. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Jullian, Valerie,Monjardet-Bas, Veronique,Fosse, Celine,Lavielle, Solange,Chassaing, Gerard
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p. 1677 - 1684
(2007/10/03)
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- Synthesis, structure and AM1 conformational study of [3]paracyclo[3](1,3)indolophane, a novel chiral cyclophane
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The title compound 5 was synthesized in seven steps with an overall yield of 22%. The two bridges were formed by a conjugate addition of indole to a Michael acceptor and by an intramolecular N-alkylation, respectively. A dynamic NMR study revealed the presence of a conformational process with an activation barrier of 10.9±0.2 kcal/mol, which was assigned to a ring flipping process that interconverts two enantiomeric sets of equilibrating bridge conformers. In the crystal structure of 5, both bridges adopt the pseudo-chair conformation, in accord with the lowest energy conformation identified by an AM1 conformational search.
- Bodwell, Graham J.,Li, Jiang,Miller, David O.
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p. 12939 - 12956
(2007/10/03)
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- Synthesis and biological activities of [E]-5-(2-acylvinyl)uracils
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The synthesis of a number of 5-substituted uracils, eg [E]-5-(2-acylvinyl)uracils 8a-8g is described. These compounds were found to have cytotoxic activities against CCRF-CEM human lymphoblastoid cells, HT-29 colon carcinoma cells and L1210/0 mouse leukemia cells. These compounds were also found to inhibit thymidylate synthase.
- Kundu,Dasgupta,Chaudhuri,Mahanty,Spears,Shahinian
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p. 473 - 479
(2007/10/02)
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- THE KINETIC ISOTOPE EFFECT IN THE REACTIONS OF SUBSTITUTED β-CHLOROPROPIOPHENONES WITH AMINES
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The kinetics of the reaction of substituted β-chloropropiophenones (RC6H4COCH2CH2Cl) and their α,α-deuterated analogs (RC6H4COCD2CH2Cl) with a series of amines in acetonitrile at 25 deg C were studied.It was shown that the relationships between the kinetic isotope effect H/kD)> and the pKa values of the amines for the substituted β-chloropropiophenones pass through a maximum and have various curvatures.The obtained dependence of kH/kD on the nature of the substituent in the substrate (?0) has complicated nonlinear character.Possible reasons for such relationships are discussed.
- Popov, A. F.,Matvienko, V. N.,Piskunova, Zh. P.
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p. 1158 - 1161
(2007/10/02)
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- Preparation and Reactivities of (η3-1- and 2-Trimethylsiloxyallyl)Fe(CO2)NO Complexes. Intermediates Functioning as Equivalents of β- and α-Acyl Carbocations and Acyl Carbanions
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(η3-1- and 2-Trimethylsiloxyallyl)Fe(CO)2NO complexes were prepared by the reaction of the corresponding siloxyallylic halides with Bu4N.These complexes reacted with both of carbon nucleophiles and carbon electrophiles preferentially at the less hindered sites of the allylic ligands.In these reactions, (η3-1-trimethylsiloxyallyl)Fe(CO)2NO complexes served as synthetically equivalent synthons for both of β-acyl carbocations and β-acyl carbanions and (η3-2-trimethylsiloxyallyl)Fe(CO)2NO complexes as both of α-acyl carbocations and α-acyl carbanions.The stereochemical courses of the reactions are described.
- Itoh, Keiji,Nakanishi, Saburo,Otsuji, Yoshio
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p. 2965 - 2977
(2007/10/02)
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- EFFECT OF THE STRUCTURE OF THE REAGENTS ON THE FORMATION RATE OF ARYL VINYL KETONES IN THE REACTION OF AMINES WITH β-HALOGENOPROPIOPHENONES
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The dependence of the formation rate of aryl vinyl ketones in the reaction of ring-substituted β-halogenopropiophenones with various amines on the structure of the reagents was investigated.By analysis of the obtained data it was concluded that the process takes place by an E2 mechanism through an anion-like transition state.
- Popov, A. F.,Piskunova, Zh. P.,Matvienko, V. N.
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p. 1918 - 1921
(2007/10/02)
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- Palladium-Catalyzed Acylation of Unsaturated Halides by Anions of Enol Ethers
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Zinc salts of enol ether anions are coupled to aryl and alkenyl halides by using palladium catalysts, effecting a direct acetylation of aryl and alkenyl halides.Zinc salts of allenic ethers are coupled with aryl and alkenyl halides under similar conditions to give α,β-unsaturated ketones, the allenic ether serving as a source of the acryloyl group.Allenic ethers were γ arylated in a palladium-catalyzed coupling with aryl halides to give β,β-diaryl-α,β-unsaturated aldehydes.
- Russell, Charles E.,Hegedus, Louis S.
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p. 943 - 949
(2007/10/02)
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- THE REACTION OF 3-(1-IMIDAZOLYL)-2-ALKEN-1-ONES WITH ORGANOMETALLIC COMPOUNDS
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In the reaction with organometallic compounds, 3-(1-imidazolyl)-2-alken-1-ones (1) gave both 1,2 and 1,4-addition products in a comparable ratio.This fact showed that the chemical properties of 1 were analogous to those of 3-phenyl-2-alken-1-ones (2) and 3-amino-2-alken-1-ones (3).
- Kashima, Choji,Tajima, Tadakuni,Omote, Yoshimori
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p. 1811 - 1814
(2007/10/02)
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