- Sc(OTf)3a'Catalyzed Ca'C Bond-Forming Reaction of Cyclic Peroxy Ketals for the Synthesis of Highly Functionalized 1,2-Dioxene Endoperoxides
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A new and general Sc(OTf)3-catalyzed C-C bond-forming reaction of 3-(2-methoxyethoxy)-endoperoxy ketals with silyl ketene acetals, silyl enol ethers, allyltrimethylsilane, and trimethylsilyl cyanide has been developed via the reactive peroxycarbenium ions, affording a wide range of complicated 3,3,6,6-tetrasubstituted 1,2-dioxenes bearing adjacent quaternary carbons and 3-acetyl/allyl/cyano functional groups in good yields at room temperature. Notably, the resultant 1,2-dioxenes are structurally stable, which can be facially transformed into another important 1,2-dioxane endoperoxide under conventional hydrogenation conditions without deconstructing the weak O-O bond.
- Feng, Haowei,Zhao, Yukun,Liu, Pengkang,Hu, Lin
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supporting information
p. 1632 - 1637
(2021/03/08)
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- Oxidative asymmetric formal aza-Diels–Alder reactions of tetrahydro-β-carboline with enones in the synthesis of indoloquinolizidine-2-ones
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Ru-catalyzed tandem amine oxidative dehydrogenation/formal aza-Diels–Alder reaction for enantio- and diastereoselective synthesis of indoloquinolizidine-2-ones from tetrahydro-β-carbolines and α,β-unsaturated ketones is described. The reaction proceeds via tandem ruthenium-catalyzed amine dehydrogenation using tert-butyl hydroperoxide (TBHP) as the oxidant and a chiral thiourea-catalyzed formal aza-[4 + 2] cycloaddition, providing a step-economical strategy for the synthesis of these valuable heterocyclic products.
- Wu, Xiang,Zhao, Shi-Bao,Zheng, Lang-Lang,Li, You-Gui
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supporting information
(2018/09/10)
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- Discovery and optimization of novel benzothiophene-3-carboxamides as highly potent inhibitors of Aurora kinases A and B
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Aurora kinases as regulators of cell division have become promising therapeutic targets recently. Here we report novel, low molecular weight benzothiophene-3-carboxamide derivatives designed and optimized for inhibiting Aurora kinases. The most effective compound 36 inhibits Aurora kinases in vitro in the nanomolar range and diminishes HCT 116 cell viability blocking cytokinesis and inducing apoptosis. According to western blot analysis, the lead molecule inhibits Aurora kinases equipotently to VX-680 (Tozasertib) and similarly synergizes with other targeted drugs.
- Gyulavári, Pál,Szokol, Bálint,Szabadkai, István,Brauswetter, Diána,Bánhegyi, Péter,Varga, Attila,Markó, Péter,Boros, Sándor,Illyés, Eszter,Szántai-Kis, Csaba,Krekó, Marcell,Czudor, Zsófia,?rfi, László
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supporting information
p. 3265 - 3270
(2018/08/24)
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- PYRIDINETHIONES, PHARMACEUTICAL COMPOSITIONS THEREOF, AND THEIR THERAPEUTIC USE FOR TREATING A PROLIFERATIVE, INFLAMMATORY, NEURODEGENERATIVE, OR IMMUNE-MEDIATED DISEASE
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Provided herein are pyridinethiones, for example, a compound of Formula I, and pharmaceutical compositions thereof. Also provided herein are methods of their use for treating, preventing, or ameliorating one or more symptoms of a proliferative, inflammatory, neurodegenerative, or immune-mediated disease (e.g., multiple sclerosis).
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Paragraph 0591; 0592
(2017/12/15)
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- Catalytic Asymmetric Conjugate Addition of Indolizines to α,β-Unsaturated Ketones
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A catalytic enantioselective conjugate addition of indolizines to enones is described. The chiral phosphoric acid (S)-TRIP activates α,β-unsaturated ketones, thereby promoting an enantioface-differentiating attack by indolizines. Using this reaction, several alkylated indolizines were synthesized in good yields and with enantiomeric ratios of up to 98:2.
- Correia, José Tiago Menezes,List, Benjamin,Coelho, Fernando
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supporting information
p. 7967 - 7970
(2017/06/27)
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- Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates
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Trialkylsilyl enol ethers are versatile intermediates often used as enolate surrogates for the synthesis of carbonyl compounds. Yet there are no reports of broadly applicable, catalytic methods for the synthesis of chiral silyl enol ethers carrying latent functionalities useful for synthetic operations beyond the many possible reactions of the silyl enol ether moiety itself. Here we report a general procedure for highly catalytic (substrate:catalyst ratio up to 1000:1) and enantioselective (92% to 98% major enantiomer) synthesis of such compounds bearing a vinyl group at a chiral carbon at the β-position. The reactions, run under ambient conditions, use trialkylsiloxy-1,3-dienes and ethylene (1 atm) as precursors and readily available (bis-phosphine)-cobalt(II) complexes as catalysts. The silyl enolates can be readily converted into novel enantiopure vinyl triflates, a class of highly versatile cross-coupling reagents, enabling the syntheses of other enantiomerically pure, stereodefined trisubstituted alkene intermediates not easily accessible by current methods. Examples of Kumada, Stille, and Suzuki coupling reactions are illustrated.
- Biswas, Souvagya,Page, Jordan P.,Dewese, Kendra R.,RajanBabu
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supporting information
p. 14268 - 14271
(2015/12/01)
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- Design, synthesis and biological evaluation of novel C3-functionalized oxindoles as potential Pim-1 kinase inhibitors
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A novel series of C3-functionalized oxindoles, 3-(2-oxo-4-phenylbut-3-en-1-ylidene)indolin-2-ones, were designed, synthesized and investigated for inhibition of cell proliferation against different types of human cancer cell lines, including SW620, HeLa and A549. This biological study showed that these compounds containing the scaffolds of indole and aromatic α,β-unsaturated ketone had moderate to significant antitumor activities. Further study suggested that compound 4b, as one of this kind of structure derivative, showed broad-spectrum antitumor activities against MCF-7, PC-3, SKOV-3, U87, SMMC-7721, SY5Y and A875 cancer cell lines. Besides, the results of the inhibition of Pim kinases indicated that compound 4b showed selective and efficient anti-Pim-1 kinase activity (IC50 = 5 μM). Docking simulation, flow cytometry (FCM), and Hoechst 33342 staining assay suggested that the most active compound 4b induced cell death through apoptosis via binding to the active ATP pocket of Pim-1. Moreover, it showed that compound 4b had strong inhibition of tubulin polymerization which may be caused by inhibiting Pim-1. This journal is
- Sun, Hong-Bao,Wang, Xiao-Yan,Li, Guo-Bo,Zhang, Li-Dan,Liu, Jie,Zhao, Li-Feng
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p. 29456 - 29466
(2015/04/14)
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- Unusual enantioselectivities in heterogeneous organocatalyzed reactions: Reversal of direction using proline di- versus tri-peptides in the aldol addition
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The heterogeneous asymmetric direct aldol reactions between aldehydes (2-nitrobenzaldehyde, 2-methylpropanal) and ketones (acetone, cyclohexanone) in the presence of polystyrene (PS) resin supported di- and tripeptides were studied under otherwise identic
- Szollosi, Gy?rgy,Csámpai, Antal,Somlai, Csaba,Fekete, Mónika,Bartók, Mihály
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- Improved conditions for the proline-catalyzed aldol reaction of acetone with aliphatic aldehydes
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The proline-catalyzed asymmetric aldol reaction between aliphatic aldehydes and acetone has, to date, remained underdeveloped. Challenges in controlling this reaction include avoiding undesired side reactions such as aldol condensation and self-aldolization. In recent years we have developed optimized conditions, which enable high yields and good to excellent enantioselectivities, and which are presented in this communication. Georg Thieme Verlag Stuttgart New York.
- Martínez, Alberto,Zumbansen, Kristina,D?hring, Arno,Van Gemmeren, Manuel,List, Benjamin
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supporting information
p. 932 - 934
(2014/05/06)
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- Reversal of enantioselectivity in aldol reaction: New data on proline/λ-alumina organic-inorganic hybrid catalysts
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We report new results on the aldol reactions between aldehydes of three different types (aromatic, aliphatic and cycloaliphatic) and acetone/cycloalkanones as reaction partners, driven by organic-inorganic hybrid catalyst Pro/λ-Al2O3. In contrast to the homogeneous liquidphase reaction, over Pro/λ-Al2O 3reversal of the enantioselection in up to 20-40 % ee depending on the structure of the aldehyde was observed in reactions of acetone. Reversal of the ee in the presence of c-Al2O3cannot be generalized, as it has only been observed for acetone among the ketones studied by us. It was proven using methods of a great variety such as ultrasonic irradiation, reuse measurements on used catalyst and the filtrate of the first reaction, measurements on the L-Pro-L-Pro(OH) dipeptide, studies using mixtures of L-Pro and D-Pro that the organic-inorganic hybrid catalyst Pro/λ-Al 2O3formed in situ is responsible for reversal of the ee. In the reactions of cycloalkanones there is presumably competition between the liquid-phase and the surface reaction over Pro/ c-Al2O 3with preference for the former. Based on these results a surface reaction pathway was proposed. Although, the ees obtained under heterogeneous catalytic conditions are low, further studies may lead to application of this unusual phenomenon for obtaining chiral heterogeneous catalysts suitable for the preparation of the desired enantiomer of a chiral compound using the same chiral source. Springer Science+Business Media New York 2013.
- Sz?ll?si, Gyo?rgy,Fekete, Mónika,Gurka, András A.,Bartók, Mihály
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p. 478 - 486
(2014/06/24)
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- Reversal of the enantioselectivity in aldol addition over immobilized di- and tripeptides: Studies under continuous flow conditions
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Heterogeneous asymmetric direct aldol reactions between aldehydes (2-nitrobenzaldehyde, 2-methylpropanal) and acetone catalyzed by polystyrene resin (PS) supported di- and tripeptides H-Pro-Pro-, H-Pro-Pro-Pro-, H-Pro-Glu(OH)-, H-Pro-Pro-Glu(OH)-, H-Pro-Asp(OH)-, H-Pro-Pro-Asp(OH)-, H-Ser-Glu(OH)-, H-Ser-Ser-Glu(OH)-, H-Val-Glu(OH)-, H-Val-Val-Glu(OH)-MBHA-PS, were studied under identical experimental conditions at room temperature in a continuous-flow fixed-bed reactor (CFBR) system. In the asymmetric aldol reactions reversal of enantioselectivity was observed on H-Pro-Pro-Glu(OH)- and H-Pro-Pro-Asp(OH)-MBHA-PS-supported catalysts (ee 42-67% S) as compared to the H-Pro-Glu(OH)- and H-Pro-Asp(OH)-MBHA-PS-supported catalyst (ee 28-82% R). In the case of H-Pro-Pro- and H-Pro-Pro-Pro-MBHA-PS-supported catalysts reversed enantioselectivity was observed by using the benzoic acid additive (12% S) as compared to the H-Pro-MBHA-PS catalyst (25% R). The stability of the catalysts in the flow system was consistent with the heterogeneous character of the reaction, as was the linear behavior obtained using mixtures of l- and d-enantiomers of the supported H-Pro-MBHA-PS catalyst. The enamine character of the reaction intermediates was supported by ESI-MS measurements. Based on these and the computed structure of the peptides, the conformation of the intermediate adducts is held responsible for chiral induction, therefore for the enantioselectivity inversion observed in these reactions.
- Gurka, Andrs,Bucsi, Imre,Kovcs, Lenke,Szollosi, Gy?rgy,Bartk, Mihly
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p. 61611 - 61618
(2015/02/19)
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- Total synthesis of (±)-hibiscone C
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A total synthesis of (±)-hibiscone C, one member of the furanosteroid family of natural products that also includes viridin and wortmannin, is reported. Two new pathways for formation of the key diacyl furan subunit are described.
- Ungureanu, Sinziana,Meadows, Maggie,Smith, Joel,Duff, David B.,Burgess, James M.,Goess, Brian C.
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scheme or table
p. 1509 - 1511
(2011/06/10)
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- Large-scale synthesis of immunoactivating natural product, pristane, by continuous microfluidic dehydration as the key step
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(Figure Presented) An efficient protocol of dehydration was developed under microfluidic conditions. The method was applied to a multikilogram synthesis of pristane, a biologically important natural product, which is now widely used as an adjuvant for monoclonal antibody production.
- Tanaka, Katsunori,Motomatsu, Shinya,Koyama, Koichi,Tanaka, Shin-Ichi,Fukase, Koichi
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p. 299 - 302
(2007/10/03)
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- Palladium catalyzed reductive decarboxylation of allyl α-alkenyl- β-ketoesters. A new synthesis of (E)-3-alkenones
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The reductive decarboxylation of α-alkenyl derivatives of allyl-β-ketoesters was achieved by use of palladium(0) catalyst generated in situ from Pd(OAc)2 and PPh3, with triethylammonium formate as the hydride source, in THF. The reaction proceeds smoothly and cleanly, with linear alkenyl derivatives of allyl-β-ketoesters, to afford (E)-3-alkenones in good to excellent yields (73-92%) and high stereoselectivity (>98%).
- Ragoussis, Valentine,Giannikopoulos, Alexandros
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p. 683 - 687
(2007/10/03)
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- L-proline-catalyzed one-pot three-component reaction for the synthesis of β-alkoxy ketones
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β-Alkoxy ketones were prepared by a one-pot three-component reaction of aliphatic aldehydes, ketones, and alcohols catalyzed by L-proline. Steric effects on the reaction were studied with substituted ketones, aldehydes, and alcohols, and the results indicate that reactions employing methyl ketones, α-unsubstituted aliphatic aldehydes and methanol produce the β-alkoxy ketones in the best yields when L-proline is used as the catalyst. The reaction mechanism is discussed. Georg Thieme Verlag Stuttgart.
- Dodda, Rajasekhar,Zhao, Cong-Gui
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p. 3238 - 3242
(2008/09/17)
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- Processes for preparing beta-hydroxy-ketones and alpha,beta-unsaturated ketones
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Processes for producing β-hydroxy-ketones and α,β-unsaturated ketones are disclosed which comprise the crossed condensation of an aldehyde with a ketone in the presence of a hydroxide or alkoxide of alkali metal or an alkaline earth metal as catalyst. The products of the process, β-hydroxy-ketones and α,β-unsaturated ketones, are useful for the preparation of many commercially important products in the chemical process industries including solvents, drug intermediates, flavors and fragrances, other specialty chemical intermediates.
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- Processes for the preparation of higher molecular weight ketones
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Processes for producing higher molecular weight ketones are disclosed that include the steps of feeding an aldol catalyst solution, a lower molecular weight aldehyde, and a lower molecular weight ketone, through a reactor provided with a solid hydrogenation catalyst and hydrogen gas; recovering a liquid reactor effluent containing the higher molecular weight ketone as a reaction product; and recycling a portion of the recovered liquid reactor effluent back through the reactor.
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- Proline-catalyzed ketone-aldehyde aldol reactions are accelerated by water
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Proline-catalyzed aldol reactions between acetone or 4-thianone and different aldehydes are accelerated by addition of 1-10 equivalents of water to the reaction medium, allowing stoichiometric aldol reactions to proceed at acceptable rates.
- Nyberg, Annika I.,Usano, Annina,Pihko, Petri M.
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p. 1891 - 1896
(2007/10/03)
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- Synthesis of new chiral auxiliaries for 6π-azaelectrocyclization: 4- and 7-alkyl substituted cis-1-amino-2-indanols
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The synthesis of new chiral auxiliaries, 7-alkyl substituted cis-1-amino-2-indanol derivatives, was established by the Diels-Alder reaction of 1-substituted dienes with cyclopentenone followed by the asymmetric epoxidation of the resulting indene derivatives and then the Ritter reaction. These bulky cis-aminoindanol derivatives are very effective as chiral auxiliaries and nitrogen sources in the asymmetric 6π-azaelectrocyclization. The corresponding 4-alkyl derivative was also prepared using a similar method.
- Kobayashi, Toyoharu,Tanaka, Katsunori,Miwa, Junichi,Katsumura, Shigeo
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p. 185 - 188
(2007/10/03)
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- Development of highly stereoselective asymmetric 6π- azaelectrocyclization of conformationally flexible linear 1-azatrienes. From determination of multifunctional chiral amines, 7-alkyl cis-1-amino-2-indanols, to application as a new synthetic strategy: Formal synthesis of 20-epiuleine
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The highly stereoselective asymmetric 6π-azaelectrocyclization was achieved as a general synthetic method based on the reaction between the (E)-3-carbonyl-2,4,6-trienal compounds and the (-)-7-alkyl-cis-l-amino-2-indanol derivatives which are effective chiral amines. The 7-alkyl-substituted 2-indanol moiety of the cyclized products was efficiently removed by the novel manganese dioxide oxidation under remarkably mild conditions, and the method was successfully applied to the formal synthesis of optically active 20-epiuleine.
- Tanaka, Katsunori,Kobayashi, Toyoharu,Mori, Hajime,Katsumura, Shigeo
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p. 5906 - 5925
(2007/10/03)
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- Dynamic kinetic resolution of allylic alcohols mediated by ruthenium- and lipase-based catalysts.
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An enzyme-metal combo reaction has been developed for the dynamic kinetic resolution of allylic alcohols in which racemic substrates are transformed by a lipase and a ruthenium complex in the presence of an acyl donor to allylic acetates of high optical purity in over 80% yield.
- Lee,Huh,Kim,Jung,Koh,Park
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p. 2377 - 2379
(2007/10/03)
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- β-Carbonyl substituted glutathione conjugates as inhibitors of O. volvulus GST2
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A series of β-carbonyl substituted glutathione conjugates were prepared and evaluated as inhibitors of OvGST2. Their specificity for the parasite derived protein was assessed through comparison with their inhibition of human πGST. Inhibition of OvGST2 has been demonstrated at low micromolar concentrations for these conjugates and selectivity for OvGST2 over human π-GST of greater than 10-fold has been achieved. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Brophy, Peter M.,Campbell, Alison M.,Van Eldik, Annamaria J.,Teesdale-Spittle, Paul H.,Liebau, Eva,Wang, Meng F.
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p. 979 - 981
(2007/10/03)
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- Facile transformation of N,N-dimethylhydrazones and tosylhydrazones to ketones with dimethylsulfate and potassium carbonate
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N,N-Dimethylhydrazones and tosylhydrazones can be converted to their ketones in good to excellent yields with dimethylsulfate and K2CO3.
- Kamal, Ahmed,Arifuddin,Rao, N. Venugopal
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p. 3927 - 3931
(2007/10/03)
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- Method for the synthesis of α β-unsaturated ketones
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The present invention relates to a method for the synthesis of α, β-unsaturated ketones which comprises, in the method for the synthesis of α, β-unsaturated ketones represented by general formula STR1 reacting aldehydes represented by general formula (where R1 is as defined above) with alkali metal salt of acetoacetic acid represented by general formula STR2 (where M≈ is an alkali metal ion), in the presence as a catalyst of 3-azabicyclo[3,2,2]nonane, a cyclic secondary amine represented by general formula (1) STR3 a cyclic secondary amine represented by general formula (2) STR4 (where, l is 1 or more and up to 6, a ring with N is a 6-membered, 7-membered or 8-membered ring, the two neighbors of N are methylene, R3 is a lower alkyl group, its substitution position is at a carbon atom other than two those adjacent to N, and STR5 is an alicyclic group or a phenol group), or a secondary amine represented by general formula (3) in a mixuture solvent of water and water-insoluble organic solvent, while keeping the pH constant with mineral acid, and by adjusting an amount of water.
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- REACTION OF HOMOALLYLIC COMPOUNDS OF TIN WITH ACYLATING AGENTS
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In the reaction of homoallylic organotin compounds with carboxylic acid anhydrides and chlorides in the presence of Lewis acids cyclopropyl methyl ketones are formed with α,β-unsaturated ketones and β-chloro ketones as impurities.The ratio of the reaction products depends on the temperature, the structure of the reagents, and the type of catalyst.
- Ivashchenko, N. B.,Polunin, E. V.,Kashin, A. N.
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p. 546 - 550
(2007/10/02)
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- Knoevenagel Reactions with β-Oxo Acids. Regiospecific Enol Equivalents for Syntheses of α,β-Unsaturated Ketones and of Some β-Ketols
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3-Oxobutanoic acid reacts with aliphatic aldehydes in the presence of pyridine to give α,β-unsaturated methyl ketones in good yields.Analogous results were obtained with a series of other β-oxo acids.Synthesis of (E)-7-methyloct-4-en-3-one, a major constituent of the marine sponge Plakortis zygompha, has been carried out using this methodology.Aromatic aldehydes are generally less reactive under these conditions but give β-ketols when the phenyl ring bears an electron-withdrawing substituent.Some observations on the mechanism of the reaction between 3-oxobutanoic acid and benzaldehyde are presented.
- Grayson, David H.,Tuite, Mathew R. J.
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p. 2137 - 2142
(2007/10/02)
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- 1-Oxoalkyl-2-isopropylnorbornane derivatives, uses thereof in augmenting or enhancing the aroma of consumable materials and processes for preparing same
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Described are 1-oxoalkyl-2-isopropylnorbornane derivatives defined according to the generic structure: STR1 wherein X represents a moiety selected from the group consisting of: STR2 wherein the dashed line represents a carbon-carbon double bond or a carbon-carbon single bond and wherein R1 and R2 represent hydrogen or methyl with the proviso that R1 and R2 are not both methyl, and uses thereof in augmenting or enhancing the aroma of consumable materials selected from the group consisting of perfume compositions, colognes and perfumed articles. Also described are processes for preparing said 1-oxoalkyl-2-isopropylnorbornane derivatives by means of a low temperature catalytic Diels Alder reaction or high temperature thermal Diels Alder reaction between a bicyclopentadiene derivative and 2-methyl-3- buten-5-one according to the reaction: STR3 wherein R represents methyl or hydrogen.
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- Equilibration of 5-Methyl-3-hexen-2-one and 5-Methyl-3-hexen-2-one and of XCH2CH=CYZ/XCH=CHCHYZ Pairs in General
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The equilibrium constant for isomerization of 5-methyl-4-hexen-2-one to trans-5-methyl-3-hexen-2-one in tert-butyl alcohol at 25 deg C has been found to be 0.40, which is smaller by 250-fold than a literature value.This and other equilibrium constants for reactions of the type XCH2CH=CMe2 XCH=CHCHME2 are shown to be consistent with the double bond stabilizing abilities of various groups as measured by equilibrium constants for reactions of the type XCH2CH=CHY XCH=CHCH2Y.The general case of isomerizations of the type XCH2CH=CYZ XCH=CHCHYZ is also discussed.
- Hine, Jack,Linden, Shwn-Meei
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p. 584 - 587
(2007/10/02)
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- A New Route to 5-Substituted Resorcinols and Related Systems
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Michael-type additions of phenylsulphinylacetate esters to αβ-unsaturated ketones produce cyclohexane-1,3-dione derivatives, which, after thermal elimination of benzenesulphenic acid, give the corresponding 5-substituted resorcinols, such as olivetol.The scope of this entry into other aromatic systems, such as 3,5-disubstituted and 2,3,5-trisubstituted phenols and orsellinic acid has been explored.
- Jaxa-Chamiec, Albert A.,Sammes, Peter G.,Kennewell, Peter D.
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p. 170 - 175
(2007/10/02)
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- Production of α,β-unsaturated ketones
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A process for the production of α,β-unsaturated ketones by reaction of an aldehyde with a ketone in the presence of a catalyst consisting essentially of zinc oxide in the liquid phase. The ketones obtained are suitable in some cases as solvents and in some cases as intermediates for the production of valuable odorants, dyes, plastics and especially natural substances.
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