Beta-unsaturated Ketones Research Articles

Assessment of functional group in herbal formulation sathakuppai chooranam through fourier transform infrared spectroscopy

Background: The Sathakuppai chooranam is a single herbal medicine used in the treatment of Kumbavatham (Periarthritis). Objective: This study is aimed to evaluating the morphology and elemental charecterization of the Sathakuppai chooranam. Materials and methods: The ingredients were collected and purified and the drug was prepared as per Siddha literature Siddha Vaithiya Pathartha Guna vilakkam. It is subjected into characterisation through FT-IR analysis. Results: The FT-IR characterization showed the presence of functional groups like O-H stretching (carboxylic acid, alcohol molecule), N-H stretching (amine salt),C-H stretching (alkene), N-H stretching (amine salt), C-H stretching (alkene),C=C stretching (conjugate alkene, cyclic alkene,alpha beta unsaturated ketone), N=H bending (amine),O-H bending (carboxylic acid, alcohol),C-O stretching (alkyl aryl ether, primary alcohol), C-N stretching (amine), S=O stretching (sulfoxide), C=C bending (alkene), C-Br stretching (halo compund)which ensures the therapeutic effect of drug. Conclusion: The instrumental analysis FT-IR study for Sathakuppai chooranam shows the presence of functional groups through the stretch and bends which is responsible for its functional activity. The functional groups present in Sathakuppai Chooranam have analgesic, anti-inflammatory activities. This will ensure the efficacy and therapeutic effect of Sathakuppai Chooranam. This study forms the base for the pharmaceutical analysis of the Sathakuppai Chooranam.

Chemoselective reduction for different steroidal alpha, beta-unsaturated ketone into diene by using Luche reagent

Chemoselective reduction for different steroidal alpha, beta-unsaturated ketone into diene by using Luche reagent

Chinese Medicine for Treating Endocrinology-Related Disease

Chinese Medicine for Treating Endocrinology-Related Disease

ChemInform Abstract: Synthesis of Functionalized Indoles with a Trifluoromethyl‐Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel—Crafts Alkylation with β‐Trifluoromethyl‐α,β‐enones.

Chiral complexes of BINOL-based ligands with zirconium tert-butoxide catalyze the Friedel-Crafts alkylation reaction of indoles with beta-trifluoromethyl-alpha,beta-unsaturated ketones to give functionalized indoles with an asymmetric tertiary carbon center attached to a trifluoromethyl group. The reaction can be applied to a large number of substituted alpha-trifluoromethyl enones and substituted indoles. The expected products were obtained with good yields and ees of up to 99%.

ChemInform Abstract: Stereoselective Construction of Halogenated Quaternary Stereogenic Centers via Catalytic Asymmetric Diels—Alder Reaction.

Highly enantioselective Diels-Alder reactions of alpha-halo-alpha,beta-unsaturated ketones with Lewis acid-activated chiral oxazaborolidine 1 are described. The reaction with alpha-fluoroenones provided the corresponding cyclohexane derivatives having a fluorinated quaternary stereogenic center with up to 99% de and 94% ee. The reaction with alpha-bromo cyclic enones provided the corresponding bromo bicyclic adducts with up to 99% de and 95% ee. A brominated cis-fused bicyclic adduct derived from 2-bromocyclopenten-1-one and Dane's diene was converted to the trans-fused bicyclic system via reductive alkylation with the bulky aluminum reagent aluminum tris(2,6-diphenylphenoxide) (ATPH). With this process, formal syntheses of (+)-estrone and norgestrel have been demonstrated.

Synthesis of Functionalized Indoles with a Trifluoromethyl‐Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel–Crafts Alkylation with β‐Trifluoromethyl‐α,β‐enones

Chiral complexes of BINOL-based ligands with zirconium tert-butoxide catalyze the Friedel-Crafts alkylation reaction of indoles with beta-trifluoromethyl-alpha,beta-unsaturated ketones to give functionalized indoles with an asymmetric tertiary carbon center attached to a trifluoromethyl group. The reaction can be applied to a large number of substituted alpha-trifluoromethyl enones and substituted indoles. The expected products were obtained with good yields and ees of up to 99%.

Applications of Allylsamarium Bromide as a Grignard Reagent and a Single‐Electron Transfer Reagent in the One‐Pot Synthesis of Dienes and Trienes

The utility of allylsamarium bromide, both as a nucleophilic reagent and a single-electron transfer (SET) reagent in the reaction of alpha-halo, gamma-halo-alpha,beta-unsaturated ketones and esters with allylsamarium bromide is reported for the first time in this paper. From a synthetic point of view, a general, efficient and experimentally simple one-pot method for the preparation of 1,4-dienes and trienes is developed. A possible mechanism of the transformation is proposed.

Iron-catalyzed regio- and stereoselective addition of acid chlorides to alkynes

An iron-catalyzed regio- and stereoselective addition of acid chlorides to alkynes has been described. The reaction utilizes an inexpensive iron catalyst system and it is suitable for the formation of a variety of bifunctional molecules. This is an inexpensive, regio-, stereoselective and atom-economical approach to beta-chloro-alpha,beta-unsaturated ketones from simple and readily available starting materials.

A Tandem Reaction Initiated by 1,4-Addition of Bis(iodozincio)methane for 1,3-Diketone Formation

Treatment of an gamma-acyloxy-alpha,beta-unsaturated ketone with bis(iodozincio)methane leads to a novel tandem reaction consisting of three steps: (1) 1,4-addition of the dizinc reagent to the enone, which affords the corresponding zinc enolate of the beta-zinciomethylated ketone; (2) intramolecular nucleophilic attack by the enolate on the ester group; and (3) Grob-type fragmentation of the adduct, accompanied by elimination of the zinc alkoxide of allyl alcohol. The overall reaction gives 1,3-diketones efficiently.

Ethacrynic Acid Exhibits Selective Toxicity to Chronic Lymphocytic Leukemia Cells by Inhibition of the Wnt/β-Catenin Pathway

BackgroundAberrant activation of Wnt/β-catenin signaling promotes the development of several cancers. It has been demonstrated that the Wnt signaling pathway is activated in chronic lymphocytic leukemia (CLL) cells, and that uncontrolled Wnt/β-catenin signaling may contribute to the defect in apoptosis that characterizes this malignancy. Thus, the Wnt signaling pathway is an attractive candidate for developing targeted therapies for CLL.Methodology/Principal FindingsThe diuretic agent ethacrynic acid (EA) was identified as a Wnt inhibitor using a cell-based Wnt reporter assay. In vitro assays further confirmed the inhibitory effect of EA on Wnt/β-catenin signaling. Cell viability assays showed that EA selectively induced cell death in primary CLL cells. Exposure of CLL cells to EA decreased the expression of Wnt/β-catenin target genes, including LEF-1, cyclin D1 and fibronectin. Immune co-precipitation experiments demonstrated that EA could directly bind to LEF-1 protein and destabilize the LEF-1/β-catenin complex. N-acetyl-L-cysteine (NAC), which can react with the α, β-unsaturated ketone in EA, but not other anti-oxidants, prevented the drug's inhibition of Wnt/β-catenin activation and its ability to induce apoptosis in CLL cells.Conclusions/SignificanceOur studies indicate that EA selectively suppresses CLL survival due to inhibition of Wnt/β-catenin signaling. Antagonizing Wnt signaling in CLL with EA or related drugs may represent an effective treatment of this disease.

Nucleophilic Cyclopropanation Reaction with Bis(iodozincio)methane by 1,4‐Addition to α,β‐Unsaturated Carbonyl Compounds

Treatment of alpha,beta-unsaturated ketones with an electrophilic site at the gamma-position in the presence of trimethylsilyl cyanide with bis(iodozincio)methane afforded the (Z)-silyl enol ether of the beta-cyclopropyl substituted ketone in good yields. The reaction proceeds by 1,4-addition to form an enolate, and its sequential intramolecular nucleophilic attack to an adjacent electrophilic site. The reaction of gamma-ethoxycarbonyl-alpha,beta-unsaturated ketone and bis(iodozincio)methane in the presence of trimethylsilyl cyanide afforded 1-ethoxy-1-trimethylsiloxycyclopropane derivatives, which can be regarded as the homoenolate equivalent. Additionally, reaction of the obtained homoenolate equivalents with imines give 1-(E)-alkenyl-2-(1-aminoalkyl)alkanols diastereoselectively.

Flavouring Group Evaluation 220: alpha, beta‐Unsaturated ketones and precursors from chemical subgroup 4.4 of FGE.19: 3(2H)‐Furanones

Flavouring Group Evaluation 220: alpha, beta‐Unsaturated ketones and precursors from chemical subgroup 4.4 of FGE.19: 3(2H)‐Furanones

Flavouring Group Evaluation 216: alpha, beta‐Unsaturated aldehydes from chemical subgroup 3.3 of FGE.19: 2‐Phenyl‐2‐alkenals

EFSA JournalVolume 7, Issue 4 881 OpinionOpen Access Flavouring Group Evaluation 216: alpha, beta-Unsaturated aldehydes from chemical subgroup 3.3 of FGE.19: 2-Phenyl-2-alkenals European Food Safety Authority (EFSA), European Food Safety Authority (EFSA)Search for more papers by this author European Food Safety Authority (EFSA), European Food Safety Authority (EFSA)Search for more papers by this author First published: 01 April 2009 https://doi.org/10.2903/j.efsa.2009.881Citations: 1 Panel members: Arturo Anadon, David Bell, Mona-Lise Binderup, Wilfried Bursch, Laurence Castle, Riccardo Crebelli, Karl-Heinz Engel, Roland Franz, Nathalie Gontard, Thomas Haertle, Trine Husøy, Klaus-Dieter Jany, Catherine Leclercq, Jean Claude Lhuguenot, Wim Mennes, Maria Rosaria Milana, Karla Pfaff, Kettil Svensson, Fidel Toldra, Rosemary Waring, Detlef Wölfle. Acknowledgement: European Food Safety Authority wishes to thank the members of the Working Groups on Flavourings for the preparation of this opinion: Ulla Beckman Sundh, Vibe Beltoft, Wilfried Bursch, Angelo Carere, Riccardo Crebelli, Karl-Heinz Engel, Henrik Frandsen, Jørn Gry, Rainer Gürtler, Frances Hill, Trine Husøy, John Christian Larsen, Catherine Leclercq, Pia Lund, Wim Mennes, Gerard Mulder, Karin Nørby, Gerard Pascal, Iona Pratt, Gerrit Speijers, Harriet Wallin. Adoption date: 27 November 2008 Published date: 1 April 2009 Question number: EFSA-Q-2008-761 AboutPDF ToolsExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat References Benigni, R., Netzeva, T., 2007a. Report on a QSAR model for prediction of genotoxicity of alpha, beta-unsaturated aldehydes in S. typhimurium TA 100 and its application for predictions on alpha, beta-unsaturated aldehydes in Flavouring Group Evaluation 19 (FGE.19). Unpublished report submitted by FLAVIS Secretariat to EFSA. Benigni, R., Netzeva, T., 2007b. Report on a QSAR model for prediction of genotoxicity of alpha, beta-unsaturated ketones in S. typhimurium TA 100 and its application for predictions on alpha, beta-unsaturated aldehydes in Flavouring Group Evaluation 19 (FGE.19). Unpublished report submitted by FLAVIS Secretariat to EFSA. EC, 1996. Regulation No 2232/96 of the European Parliament and of the Council of 28 October 1996. Official Journal of the European Communities 23.11.1996, L 299, 1– 4. EC, 1999a. Commission Decision 1999/217/EC of 23 February 1999 adopting a register of flavouring substances used in or on foodstuffs. Official Journal of the European Communities 27.3.1999, L 84, 1– 137. EC, 2000a. Commission Regulation No 1565/2000 of 18 July 2000 laying down the measures necessary for the adoption of an evaluation programme in application of Regulation (EC) No 2232/96. Official Journal of the European Communities 19.7.2000, L 180, 8– 16. EC, 2002b. Commission Regulation No 622/2002 of 11 April 2002 establishing deadlines for the submission of information for the evaluation of chemically defined flavouring substances used in or on foodstuffs. Official Journal of the European Communities 12.4.2002, L 95, 10– 11. EC, 2008a. Commission Decision 2008/478/EC of 17 June 2008 amending Decision 1999/217/EC as regards the register of flavouring substances used in or on foodstuffs. Official Journal of the European Union 24.6.2008, L 163, 42. EFSA, 2008b. Minutes of the 26th Plenary meeting of the Scientific Panel on Food Additives, Flavourings, Processing Aids and Materials in Contact with Food, Held in Parma on 27 – 29 November 2007. Parma, 7 January 2008. [Online]. Available: www.efsa.europa.eu/EFSA/Event_Meeting/afc_minutes_26thplen_en.pdf. EFSA, 2008bb. Genotoxicity Test Strategy for Substances belonging to Subgroups of FGE.19 - Statement of the Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF). EFSA Journal (2008) 854, 1– 5. [online]. Available: www.efsa.europa.eu/EFSA/efsa_locale-1178620753812_1211902211354.htm. Gry, J., Beltoft, V., Benigni, R., Binderup, M.-L., Carere, A., Engel, K.-H., Gürtler, R., Jensen, G.E., Hulzebos, E., Larsen, J.C., Mennes, W., Netzeva, T., Niemelä, J., Nikolov, N., Nørby, K.K., Wedebye, E.B., 2007. Description and validation of QSAR genotoxicity models for use in evaluation of flavouring substances in Flavouring Group Evaluation 19 (FGE.19) on 360 alpha, beta-unsaturated aldehydes and ketones and precursors for these. Unpublished report submitted by FLAVIS Secretariat to EFSA. JECFA, 2006a. Safety evaluation of certain food additives and contaminants. Sixty-third meeting of the Joint FAO/WHO Expert Committee on Food Additives, WHO Food Additives Series: 54. IPCS, WHO, Geneva. Nikolov, N., Jensen, G.E., Wedebye, E.B., Niemelä, J., 2007. Report on QSAR predictions of 222 alpha, beta-unsaturated aldehydes and ketones from Flavouring Group Evaluation 19 (FGE.19) on 360 alpha, beta-unsaturated aldehydes and ketones and precursors for these. Unpublished report submitted by FLAVIS Secretariat to EFSA. SCF, 1999. Opinion on a programme for the evaluation of flavouring substances (expressed on 2 December 1999). Scientific Committee on Food. SCF/CS/FLAV/TASK/11 Final 6/12/1999. Annex I the minutes of the 119th Plenary meeting. European Commission, Health & Consumer Protection Directorate-General. Citing Literature Volume7, Issue4April 2009881 ReferencesRelatedInformation

β′‐Hydroxy‐α,β‐unsaturated ketones: A new pharmacophore for the design of anticancer drugs. Part 2.

Novel antiproliferative beta'-acyloxy-alpha,beta-unsaturated ketones were obtained by means of an iron(III)-catalyzed multicomponent domino process (ABB' 3CR). The most active derivatives displayed GI(50) values in the range of 0.5-3.9 muM against a panel of representative human solid tumor cell lines: A2780, SW1573, HBL-100, T-47D and WiDr. Analysis of cells following 24 h exposure to these drugs showed cell cycle arrest in the S and G(2)/M phase, in a dose-dependent manner. Our data indicate that the beta'-acyloxy-alpha,beta-unsaturated ketones cause permanent damage to the cells and induce apoptosis.

CuH-Catalyzed Enantioselective Intramolecular Reductive Aldol Reactions Generating Three New Contiguous Asymmetric Stereocenters

Treatment of beta,beta-disubstituted-alpha,beta-unsaturated ketones bearing a ketone residue with in situ generated, catalytic CuH ligated by a nonracemic ligand leads to three newly created adjacent chiral centers. Excellent de's and ee's are obtained for several examples studied.

Cu-Catalyzed Asymmetric Conjugate Additions of Dialkyl- and Diarylzinc Reagents to Acyclic β-Silyl-α,β-unsaturated Ketones. Synthesis of Allylsilanes in High Diastereo- and Enantiomeric Purity

A readily available and simple (MW = 444.5 g/mol) valine-based chiral phosphine is used to promote highly efficient catalytic asymmetric conjugate additions of dialkyl- and diarylzinc reagents to acyclic beta-silyl-alpha,beta-unsaturated ketones. The catalytic asymmetric protocol allows access to versatile allylsilanes that bear a trisubstituted olefin in high diastereo- and enantiomeric purity.

Multiple hydride reduction pathways in isoflavonoids

BackgroundIsoflavonoids are of interest owing to their appearance in metabolic pathways of isoflavones, and their estrogenic and other physiological properties, making them promising lead compounds for drug design.ResultsThe reduction of isoflavones by various hydride reagents occurs by a 1,4-pathway in contrast to ordinary β-alkoxy-α,β-unsaturated ketones. Isoflavan-4-ones, cis- and trans-isoflavan-4-ols, α-methyldeoxybenzoins or 1,2-diphenylprop-2-en-1-ols are obtained depending on the hydride reagent, mostly in good yields. The stereoselective reduction of isoflavan-4-ones is also discussed.ConclusionThe work described in this paper shows that most structural types of reduced isoflavonoids are now reliably available in satisfactory or good yields by hydride reductions to be used as authentic reference compounds in analytical and biological studies.

First Stereospecific Synthesis of (E)- or (Z)-α-Fluoroenones via a Kinetically Controlled Negishi Coupling Reaction

A highly stereospecific synthesis of (E)- or (Z)-alpha-fluoro-alpha,beta-unsaturated ketones 4, via a kinetically controlled Negishi palladium-catalyzed coupling reaction, was developed, providing an easy and general access to valuable fluorinated intermediates (pharmaceutical, peptide mimic, and so on). The synthesis involved a reaction between E/Z gem-bromofluoroolefins 2 and alkoxyvinylzinc species 6 under controlled reaction temperature. At 10 degrees C, (Z)-4 (70 to 99% yields) was obtained along with unreacted (Z)-2 (66 to 99% yields). At THF reflux, the recovered olefin was transformed into (E)-4 (up to 98% yield).

Synthesis and pharmacological screening for muscle relaxant, anticonvulsant, and sedative activities of certain Organic compounds produced by Michael addition

Michael addition of certain nucleophiles on alpha, beta-unsaturated ketones 1 led to the formation of adducts 2-7 as well as the reaction of arylidene derivatives with secondary amines afforded the amino compounds 9 and 11. Also, dialkylmalonates were treated with alpha-cyano cinnamide to afford 13. On the other hand, double Michael cycloaddition of ethylcyanoacetate or tetrachlorophthalic anhydride to the suitable divinylketone were synthesized to produce 15-17. Selected compounds (13 and 6) were screened for muscle relaxant, anticonvulsant, and sedative activities using established pharmacological models. Their activities were compared with that of phenobarbital sodium taken as standard. Compound 6 was the most potent muscle relaxant while compounds 13a and 13c offered the highest anticonvulsant activity. Meanwhile compound 13c showed the highest potentiation of phenobarbital induced sleep in mice.

6‐Endo‐Trig Mode Cyclization to a Hydrindanone Using Samarium(II) Iodide

AbstractFor Abstract see ChemInform Abstract in Full Text.