- A concise synthesis of xestospongic acid methyl ester with pancreatic lipase inhibitory activity
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Xestospongic acid methyl ester, a naturally brominated fatty acid with potent pancreatic lipase inhibitory activity in vitro, was synthesized from 5-hexynol in 30% total yield.
- Gong, Jing-Xu,Wang, He-Yao,He, Wen-Fei,Wang, Zhen-Zhong,Xiao, Wei,Guo, Yue-Wei
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- A boron-based Ireland-Claisen approach to the synthesis of pordamacrine A
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A synthetic approach to pordamacrine A that features two key transformations is discussed. The first transformation applies an Ireland-Claisen rearrangement to establish sterically congested vicinal carbon centers. Although a hard enolization technique for accessing the silyl ketene acetal failed, a soft enolization, boron-based reaction was highly successful. The second step involves a proposed cascade palladium-catalyzed biscyclization to construct two carbocycles of the natural product. The overall strategy is presented, demonstrating the challenges of the cyclization events in this complex setting.
- Seizert, Curtis A.,Ferreira, Eric M.
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- Palladium-catalysed direct synthesis of optically active dienols
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A direct and highly chemo, regio and stereocontrolled method for constructing optically active conjugated dienols is described and illustrated by a short, convenient and efficient synthesis of methyl (9R)-9-hydroxytetradeca-5Z,7E-dienoate(-)-1.
- Jeffery
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- DIMERIC IMMUNO-MODULATORY COMPOUNDS AGAINST CEREBLON-BASED MECHANISMS
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Disclosed are small molecules against cereblon to enhance effector T cell function. Methods of making these molecules and methods of using them to treat various disease states are also disclosed.
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Page/Page column 144-145
(2020/02/06)
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- Luminescence modulations of rhenium tricarbonyl complexes induced by structural variations
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Octahedral d6 low-spin Re(I) tricarbonyl complexes are of considerable interest as noninvasive imaging probes and have been deeply studied owing to their biological stability, low toxicity, large Stokes shifts, and long luminescence lifetimes. We reported recently the bimodal IR and luminescence imaging of a Re(I) tricarbonyl complex with a Pyta ligand (4-(2-pyridyl)-1,2,3-triazole) in cells and labeled such metal-carbonyl complexes SCoMPIs for single-core multimodal probes for imaging. Re(I) tricarbonyl complexes have unique photophysical properties allowing for their unequivocal detection in cells but also present some weaknesses such as a very low luminescence quantum yield in aqueous medium. Further optimizations would thus be desirable. We therefore developed new Re(I) tricarbonyl complexes prepared from different ancillary ligands. Complexes with benzothiadiazole- triazole ligands show interesting luminescent quantum yields in acetonitrile and may constitute valuable luminescent metal complexes in organic media. A series of complexes with bidentate 1-(2-quinolinyl)-1,2,3-triazole (Taquin) and 1-(2-pyridyl)-1,2,3-triazole (Tapy) ligands bearing various 4-substituted alkyl side chains has been designed and synthesized with efficient procedures. Their photophysical properties have been characterized in acetonitrile and in a H 2O/DMSO (98/2) mixture and compared with those of the parent Quinta- and Pyta-based complexes. Tapy complexes bearing long alkyl chains show impressive enhancement of their luminescent properties relative to the parent Pyta complex. Theoretical calculations have been performed to further characterize this new class of rhenium tricarbonyl complexes. Preliminary cellular imaging studies in MDA-MB231 breast cancer cells reveal a strong increase in the luminescence signal in cells incubated with the Tapy complex substituted with a C12 alkyl chain. This study points out the interesting potential of the Tapy ligand in coordination chemistry, which has been so far underexploited.
- Bertrand, Helene C.,Clede, Sylvain,Guillot, Regis,Lambert, Francois,Policar, Clotilde
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p. 6204 - 6223
(2014/07/07)
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- Synthesis and functional pharmacological effects on human bronchi of 20-hydroxyeicosatetraenoic acid
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We have synthesized 20-hydroxyeicosatetraenoic acid (20-HETE) following a new route and delineated its functional effects in human bronchi. Isometric tension measurements were performed, and they demonstrated that synthetic 20-HETE induced a concentration-dependent relaxant effect in ASM on resting tone and on bronchi pre-contracted with methacholine.
- Proteau-Gagne,St-Jean,Morin,Gendron,Rousseau,Dory
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experimental part
p. 841 - 847
(2011/04/25)
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- Preparation of large ring acetylenic lactones by iodo lactonisation
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Reaction of ω-ene-7-yne carboxylic acids with (biscollidine)iodine(I) hexafluorophosphate led to large ring acetylenic lactones. In the case of 5- or 6-yne carboxylic acids, iodo enol lactones were preferentially obtained.
- Rousseau, Gérard,Strzalko, Tekla,Roux, Marie-Claude
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p. 4503 - 4505
(2007/10/03)
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- A new base mediated method for the cleavage of tert-butyl esters
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A new method for the cleavage of tert-butyl esters with NaH in DMF is described.
- Paul, Soumendu,Schmidt, Richard R.
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p. 1107 - 1108
(2007/10/03)
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- Synthesis of ω-and (ω - 1)-acetylenic acids from five-, six-, or seven-membered cycloalkanones
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A convenient method for the synthesis of ω-and (ω - 1)-acetylenic acids involves free-radical oxidative scission of cycloalkanones containing five-, six, or seven-membered cycles to give the corresponding ω-olefinic acids followed by bromination of the latter and subsequent dehydrobromination under the action of alkalis.
- Starostin,Ignatenko,Lapitskaya,Pivnitsky,Nikishin
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p. 833 - 837
(2007/10/03)
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- Practical synthesis of hex-5-ynoic acid from cyclohexanone
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Hex-5-ynoic acid, a multipurpose synthon, was synthesized in three steps starting from cyclohexanone by bromination-dehydrobromination of the intermediate hex-5-enoic acid.
- Starostin,Lapitskaya,Ignatenko,Pivnitsky,Nikishin
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- A large scale and concise synthesis of γ-linolenic acid from 4- chlorobut-2-yn-1-ol
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A large scale and concise synthesis of γ-linolenic acid is described. The key step of the synthesis involves a copper salt mediated cross-coupling of two different alkynes and chlorobutynol.
- Durand, Sandrine,Parrain, Jean-Luc,Santelli, Maurice
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p. 1015 - 1018
(2007/10/03)
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- Hepoxilin analogs
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Compounds of the general structure STR1 are disclosed, wherein X is O, Cn, NH, or S, wherein n is 1, 2, 3 or 4; R1 is OH, CH3, CH2 OH, N3 or CH2 N3 ; R3 is H or CH3 ; R5 is Y-R2, wherein Y is a six-carbon chain optionally containing up to three double or triple bonds or a mixture of double and triple bonds up to a maximum of three; R2 is C1 -C10 alkyl OH, C1 -C10 alkyl N3 or COOR4, wherein R4 is H, a branched or unbranched C1 -C10 alkyl (including substituted alkyl radicals), cycloalkyl, preferably C5 or C6 cycloalkyl, or a five- or six-membered aryl radical (including substituted aryl radicals), i.e. R2 is COOH or an ester of R4; R6 is a seven-carbon chain optionally containing up to three double or triple bonds or a mixture of double and triple bonds up to a maximum of three; and . . . . . . indicates a single, double or triple bond. The compounds are analogs of hepoxilins and are used to modulate hepoxilin activity, for example in the control of inflammation or other processes mediated by intracellular calcium levels.
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- Synthesis and Nuclear Magnetic Resonance Studies on a Series of Synthesis Long-chain Tellurophene Fatty Esters
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The synthesis and the results of the 1H and 13C NMR spectroscopic analyses of thirteen 2,5-disubstituted tellurophene fatty esters, containing substituents of different chain lengths, and of a monosubstituted tellurophene ester are repported.The tellurophene esters are obtained by cyclization of the corresponding conjugated intermediates with Na2Te in the presence of AgOAc in methanol.The tellurophene moiety in the alkyl chain induces a deshielding effect on the protons of the adjacent methylene prtons.The shift parameters of the tellurophene moiety on the shifts of the adjacent methylene carbon atoms are also determined.
- Jie, Marcel S. F. Lie Ken,Chau, Sherman H.
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p. 2642 - 2657
(2007/10/03)
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- A Stereoselective Synthesis of 8(R) and 8(S), 11(R),12(S)-Trihydroxyeicosa-5(Z),9(E),14(Z)-Trienoic Acid from 2-Deoxy-D-Ribose
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A stereoselective synthesis of stereoisomers of the title compound from 2-deoxy-D-ribose using reductive elimination protocol as the key step is described.
- Yadav, J. S.,Vadapalli, Prahlad
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p. 641 - 644
(2007/10/02)
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- METHOD OF SELECTIVELY INHIBITING CALCIUM-INDEPENDENT MYOCARDIAL PHOSPHOLIPASE A2
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Inhibition of calcium-independent myocardial phospholipase A2 is shown for compounds of the formula: wherein R and R1 independently represent hydrogen and halogen, alkyl, alkenyl and alkynyl radicals; R2 represents aryl, aryloxy, and heteroaryl radicals; and X is 1 or 2
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- Pesticidal compounds
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The present invention provides a class of novel substituted bicyclooctanes which have pesticidal activity, particularly against arthropod pests. Pesticidal formulations containing the compounds of the formula (I), their use in the control of pests and methods for their preparation are also disclosed.
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- Eicosatriynoic acid esters and amides and their application in pharmaceutical and cosmetic practice
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Compound, corresponding to the formula in which R is a C1 -C8 lower alkoxy or C4 -C6 cycloalkoxy group, substituted with one or more hydroxyl groups and/or interrupted by one or more hetero atoms chosen from oxygen and sulphur, an amino group of structure STR1 in which R1 or R2, which may be identical or different, denote a hydrogen atom or a linear or branched C1 -C8 lower alkyl radical, optionally interrupted by one or more hetero atoms chosen from oxygen, sulphur and nitrogen, this alkyl radical being able to be substituted with one or more hydroxyl groups, R1 and R2 not being able to denote hydrogen simultaneously, or alternatively R1 and R2 form, together with the nitrogen atom, a heterocyclic system optionally containing oxygen, sulphur or nitrogen as an additional hetero atom, one of the radicals R1 and R2 also being able to denote, when the other is a hydrogen atom, an aryl radical of formula (II): STR2 or alternatively a benzyl radical of formula (III): STR3 in which formulae R3 and R4, denote, independently of each other, a hydrogen atom, a C1 -C4 alkyl radical, a hydroxyl group, a halogen atom or a carboxyl or trifluoromethyl group, the amine group also being able to originate from a sugar, and also the isomers and salts thereof which are pharmaceutically and cosmetically acceptable.
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- DIELS-ALDER REACTIVITY OF PYRANOINDOL-3-ONES. PART 3. INTRAMOLECULAR DIELS-ALDER REACTIONS.
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Heating the 1-alkynylpyranoindol-3-ones (5), prepared from the alkynoic acids (3), results in intramolecular Diels-Alder reaction involving the indole-2,3-quinodimethane diene with subsequent extrusion of carbon dioxide to give the cycloalkacarbazoles (6).The pyranoindolones need not be isolated, since the 2-acylindol-3-ylacetic acids (8) undergo cyclodehydration and intramolecular Diels-Alder reaction when heated in an acidic anhydride as solvent.In contrast to the intramolecular Diels-Alder reaction involving the acetylenic compound (5a), the olefin (9) was a much poorer substrate.
- Moody, Christopher J.,Shah, Pritom,Knowles, Philip
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p. 3249 - 3254
(2007/10/02)
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- α,β-Unsaturated Acyl Cyanides. 6. Self-Condensation and Conjugate Addition of Allyl, Allenyl-, Propargyl-, and Alkynyltrimethylsilanes
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The base-induced reaction of α,β-unsaturated acyl cyanides leads to lactones resulting from a self condensation reaction.Neutral nucleophiles such as trimethylsilyl derivatives react with α,β-unsaturated acyl cyanides in the presence of titanium tetrachloride. δ-Ethylenic acyl cyanides, δ-acetylenic acyl cyanides, γ-allenic acyl cyanides, and γ-acetylenic acyl cyanides (or the corresponding acids or methyl esters) are obtained from α,β-unsaturated acyl cyanides by condensation respectively with allyl-, allenyl-, propargyl- and alkynyltrimethylsilanes.
- Santelli, Maurice,Abed, Douniazad El,Jellal, Abdelkebir
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p. 1199 - 1206
(2007/10/02)
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- Intramolecular Reactions of N-Nitrenes with Alkynes: Conformational Anchoring in Spiro-fused 2H-Azirines
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Oxidations of N-aminoquinazolin-4(3H)-ones (7)-(11) with lead tetra-acetate in dichloromethane results in the intramolecular addition of the N-nitrene to the triple bond in each case and azirines (20), (22), (17), (23), and (30), respectively, are isolated with (31) identified as a by-product in the oxidation of compound (11).An X-ray crystal structure determination on compound (17) reveals a remarkable deformation of bond angles at the spiro centre and this feature appears to be common to all azirines.The five membered ring in the azirines (17), (20), (22), and (23) has the envelope conformation (26) and the six-membered ring in the azirine (30) has the twist-boat conformation (32): a possible explanation for this conformational anchoring is offered.
- Atkinson, Robert S.,Grimshire, Michael J.
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p. 1215 - 1224
(2007/10/02)
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- POLYMERIZATIONS OF ACETYLENES AND CYCLIC OLEFINS INDUCED BY METAL CARBYNES.
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trans-Bromotetracarbonyl(phenylmethylidyne)tungsten and related metal carbynes induce acetylenes and cycloalkenes to polymerize. The acetylenes include examples that are monosubstituted, disubstituted, and unsubstituted, as well as the first reported functionalized acetylenes in which the functional groups (the nitrile, ester, and halogen functions were studied) are not attached to the triple bond. The cycloalkenes yield polyalkenamers whose double bonds are largely cis. This last polymerization is speeded by the presence of oxygen. The stereochemistries of the polyacetylenes and the polynorbornenamer produced when the initiator is the metal carbyne are similar to those of the polymers produced when the initiator is pentacarbonyl(methoxyphenylmethylene)tungsten. A possible mechanism is presented to account for why the metal carbynes behave as though they were sources of reactive metal carbenes.
- Katz,Shih,Ying,Stuart
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p. 2659 - 2668
(2007/10/02)
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- TOTAL SYNTHESIS OF BIOLOGICALLY ACTIVE METABOLITES OF ARACHIDONIC ACID. THE TWO 8-HYDROXY-11,12(S,S)-EPOXYEICOSA-5,14(Z),9(E)-TRIENOIC ACIDS.
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An efficient and simple total synthesis of the two C(8) diastereomers of 3, of interest as possible hormonal releasing agents, is described.
- Corey, E. J.,Su, Wei-guo
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p. 5119 - 5122
(2007/10/02)
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- Synthesis of Z,Z-Skipped Diene Macrolide Pheromones for Cryptolestes and Oryzaephilus Grain Beetles (Coleoptera Cucujidae)
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Three macrolide aggregation pheromones for Cryptolestes pusillus, Cryptolestes turcicus, and Oryzaephilus mercator were synthesized stereoselectively from acyclic precursors.The first, 13-methyl-(5Z,8Z)-tridecadienolide (I), is an aggregation pheromone for C. turcicus and had been tentatively identified previously in Phoracantha synonyma.The second, 11-methyl-(3Z,6Z)-undecadienolide (II), is an aggregation pheromone for O. mercator.The third, (3Z,6Z)-dodecadienolide (III) is an aggregation pheromone for O. mercator and is also slightly attractive to C. pusillus.The racemic and enantiomeric forms of I were synthesized.
- Millar, Jocelyn G.,Oehlschlager, Allan C.
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p. 2332 - 2338
(2007/10/02)
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- Synthese der Phoracantholide K, O und M
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Two 14membered ring lactones 3 and 4 and a 12membered ring lactone 5 isolated from the metasternal secretion of the eucalypt longicorn Phoracantha synonyma have been synthesized as racemic mixtures by the following method.Reaction of the dilithium derivative of 5-hexynoic acid (6) with threo-8-bromo-2,4-isopropylidenedioxyoctane (7), followed by removal of protecting group and esterification with diazomethane gave methyl-threo-11,13-dihydroxy-5-tetradecynoate (8) (s.Scheme 2).Partial hydrogenation of the triple bond in 8 with Lindlar Pd-catalyst, followed by saponification lead to (threo,Z)-11,13-dihydroxy-5-tetradecenoic acid (10).The dihydroxy acid 10 was converted into the S-(2pyridyl) thioate and cyclized in diluted benzene solution under the influence of silver ions to yield the corresponding 12- and 14-membered lactones in approximately equal amounts.Isomerization of the mixture with p-toluenesulfonic acid in methylene chloride yielded the 14-membered lactone (cis-11,13-5Z)-11-hydroxy-5-tetradecen-13-olide almost excusively.It proved to be identical in its properties with natural phoracantholide K (3).With 5-hexynoic acid and 7-tetrahydropyranyloxy-octyl bromide or 5-tetrahydropyranyloxy-hexyl bromide as starting materials (+/-)-phoracantholide O (4) and M (5) have been synthesized in an analogous manner.
- Gerlach, Hans,Kuenzler, Peter
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p. 2312 - 2319
(2007/10/02)
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