- Syntheses of Stereochemically Restricted Lactone-type Analogues of Jasmonic Acids
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5-Oxa-7-epi-jasmonic acid and 5-oxa-jasmonic acid, which are stereochemically restricted lactone-type analogues of jasmonic acids, were synthesized via three-component coupling of 2(5H)-furanone, tert-butyl acetate and 1-bromo-2-pentyne. After acidic depr
- Toshima, Hiroaki,Aramaki, Hisateru,Ichihara, Akitami
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- Desymmetrisations of 1-alkylbicyclo[3.3.0]octane-2,8-diones by enzymatic retro-Claisen reaction yield optically enriched 2,3-substituted cyclopentanones
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A series of 1-alkylbicyclo[3.3.0]octane-2,8-diones was transformed by enzymatic retro-Claisen reaction using recombinant 6-oxocamphor hydrolase (OCH) overexpressed in Escherichia coli, to yield optically active 2,3-substituted cyclopentanones with enantiomeric excesses of up to >95%. Whilst the parent substrate, bicyclo[3.3.0]octane-2,8-dione 12, was transformed only very slowly, derivatives 13, 14, 15, 16 and 30 with alkyl chains of varying length in the 1-position were converted rapidly to optically active products with typically 82% de and up to >95% enantiomeric excess. The results confirm the apparent requirement of OCH for non-enolisable diketone substrates, and offer a potential route to decorated cyclopentanone derivatives of multiple chiral centres. Computer modelling of 1-methylbicyclo-[3.3.0]octane-2,8-dione into the active site of OCH suggested that the bicyclic [3.3.0] series substrates were accommodated in the active site in similar orientation with the natural enzyme substrate, 6-oxo-camphor, and would thus yield the (2S,3S)-product series.
- Hill, Cheryl L.,Verma, Chandra S.,Grogan, Gideon
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- The handy use of brown's p2-ni catalyst for a skipped diyne deuteration: Application to the synthesis of a [D4]-labeled F4t- neuroprostane
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Brown's P2-Ni does the job: An efficient synthesis of tetradeuterated neuroprostane (see structure) has been accomplished by using an ene-diyne stereoselective deuteration strategy.
- Oger, Camille,Bultel-Ponce, Valerie,Guy, Alexandre,Balas, Laurence,Rossi, Jean-Claude,Durand, Thierry,Galano, Jean-Marie
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- FATTY ACID DERIVATIVES AND THEIR USE
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This disclosure concerns fatty acid derivatives, pharmaceutical compositions comprising the fatty acid derivatives, and methods of using the fatty acid derivatives, for example, to treat inflammation, chronic itch, chronic pain, an autoimmune disorder, atherosclerosis, a skin disorder, arthritis, a neurodegenerative disorder, or a psychiatric disorder in a subject. In some embodiments, the fatty acid derivative is a compound, or a stereoisomer, tautomer, or pharmaceutically acceptable salt thereof, having a structure according to: (I) wherein X is from 1-16 carbons in length, Z is aliphatic from 1-16 carbons in length, or is not present, Y is selected from: (II) R1, R2, and R3 are independently hydrogen or lower alkyl, R4 is lower alkyl, hydroxyl, carboxyl, or amine, R5 is hydrogen, lower alkyl, or halide, R6 is hydroxyl or substituted thiol, and each R7 is independently hydrogen or fluoride or is not present and the adjacent carbons form alkyne.
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Page/Page column 105
(2019/01/21)
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- Synthesis of Carbolines via Palladium/Carboxylic Acid Joint Catalysis
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The combination of a Pd(0) complex with benzoic acid converts propargylic tryptamines to the corresponding tetrahydro-β-carbolines. The method uses unprotected indoles and affords the desired products with ample functional group tolerance. Detailed modeling studies reveal a close synergy between the organic and metal catalysts, which enables sequential alkyne isomerization, indole C-H activation, and eventual C-C reductive elimination to afford the target heterocycles.
- Cera, Gianpiero,Lanzi, Matteo,Balestri, Davide,Della Ca, Nicola,Maggi, Raimondo,Bigi, Franca,Malacria, Max,Maestri, Giovanni
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supporting information
p. 3220 - 3224
(2018/06/11)
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- Impaired energy processing disorders and mitochondrial deficiency
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Some aspects of the invention provide for a method of treating Impaired Energy Processing Disorders and Mitochondrial Deficiencies using polyunsaturated fatty acids which are modified in certain positions to attenuate oxidative damage by Reactive Oxygen Species (ROS) and/or suppress the rate of formation of reactive products and toxic compounds.
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Page/Page column 44
(2018/09/14)
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- ALLEVIATING OXIDATIVE STRESS DISORDERS WITH PUFA DERIVATIVES
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Some aspects of the invention provide for essential fatty acids which are substituted in specific positions to slow down oxidative damage by Reactive Oxygen Species (ROS), and to suppress the rate of consequent formation of reactive products, for the purpose of preventing or reducing the damage associated with oxidative stress associated diseases such as neurological diseases and age-related macular degeneration (AMD).
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Page/Page column 19-20
(2011/05/08)
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- Synthesis of carbazoles by gold(I)-catalyzed carbocyclization of 2-(enynyl)indoles
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A new synthetic protocol for carbazoles through gold(I)-catalyzed intramolecular hydroarylation of (Z)-2-(enynyl)indoles was achieved in good yields. The requisite (Z)-2-(enynyl)indoles were synthesized stereoselectively by trimethylgallium-promoted, Z-selective Wittig olefination of N-alkylindole-2-carboxaldehydes with propargyl ylides. Substrates possessing both alkyl as well as aromatic groups are well tolerated under these reaction conditions. Georg Thieme Verlag Stuttgart.
- Praveen, Chandrasekaran,Perumal, Paramasivan Thirumalai
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scheme or table
p. 521 - 524
(2011/04/17)
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- Stereoselective total synthesis of (+)-mueggelone, a novel inhibitor of fish development
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An efficient stereoselective total synthesis of (+)-mueggelone, a novel inhibitor of fish development, is described. Highlights of the strategy include the utilization of Sharpless asymmetric epoxidation, Yamaguchi lactonization and an olefin cross-metathesis as the key steps.
- Yadav,Somaiah,Ravindar,Chandraiah
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p. 2848 - 2850
(2008/09/20)
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- An approach to 2,3-dihydropyrroles and β-iodopyrroles based on 5-endo-dig cyclisations
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A representative series of homopropargylic sulfonamides 19 and 22b have been found to undergo smooth 5-endo-dig cyclisation upon exposure to excess iodine in acetonitrile containing potassium carbonate. The resulting 4-iodo-2,3-dihydropyrroles 23 readily react with two equivalents of DBU in DMF at 20°C to give the corresponding β-iodopyrroles 24 and 26 in excellent yields by the elimination of toluene-p-sulfinic acid. Use of less than two equivalents of base results in some loss of iodine. The iodo-2,3-dihydropyrroles 23 can be used in palladium-catalysed coupling reactions as shown by the efficient formation of the Sonogashira product 29 under mild conditions.
- Knight, David W.,Redfern, Adele L.,Gilmore, Jeremy
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p. 622 - 628
(2007/10/03)
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- Titanium(II)-based Z-reduction of alkynes. Syntheses of deuterium labelled linolenic and oleic acids and (3E,8Z,11Z)-tetradeca-3,8,11-trienyl acetate, the sex pheromone of a tomato pest, Scrobipalpuloides absoluta
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An operationally simple TiII-mediated, stereo- and regio-specific reduction of isolated, conjugated and methylene 'skipped' polyynes to the corresponding Z-polyenes in a one-pot procedure is described and applied inter alia to the syntheses of deuterium labelled linolenic and oleic acids. Final quenching with D2O (instead of H2O) results in regio- and stereo-specific Z-dideuteration of the alkyne. The synthesis of (3E,8Z,11Z)-tetradeca-3,8,11-trienyl acetate, the major sex pheromone of Scrobipalpuloides absoluta, a destructive pest of tomatoes, and the (3Z,8Z,11Z)-isomer, utilises this methodology in key reduction steps, and under- or over-reduction are negligible.
- Hungerford, Natasha L.,Kitching, William
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p. 1839 - 1858
(2007/10/03)
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- Covalent modification of cyclooxygenase-2 (COX-2) by 2-acetoxyphenyl alkyl sulfides, a new class of selective COX-2 inactivators
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All of the selective COX-2 inhibitors described to date inhibit the isoform by binding tightly but noncovalently at the substrate binding site. Recently, we reported the first account of selective covalent modification of COX-2 by a novel inactivator, 2-acetoxyphenyl hept-2-ynyl sulfide (70) (Science 1998, 280, 1268-1270). Compound 70 selectively inactivates COX-2 by acetylating the same serine residue that aspirin acetylates. This paper describes the extensive structure-activity relationship (SAR) studies on the initial lead compound 2-acetoxyphenyl methyl sulfide (36) that led to the discovery of 70. Extension of the S-alkyl chain in 36 with higher alkyl homologues led to significant increases in inhibitory potency. The heptyl chain in 2-acetoxyphenyl heptyl sulfide (46) was optimum for COX-2 inhibitory potency, and introduction of a triple bond in the heptyl chain (compound 70) led to further increments in potency and selectivity. The alkynyl analogues were more potent and selective COX-2 inhibitors than the corresponding alkyl homologues. Sulfides were more potent and selective COX-2 inhibitors than the corresponding sulfoxides or sulfones or other heteroatom-containing compounds. In addition to inhibiting purified COX-2, 36, 46, and 70 also inhibited COX-2 activity in murine macrophages. Analogue 36 which displayed moderate potency and selectivity against purified human COX-2 was a potent inhibitor of COX-2 activity in the mouse macrophages. Tryptic digestion and peptide mapping of COX-2 reacted with [1-14C-acetyl]-36 indicated that selective COX-2 inhibition by 36 also resulted in the acetylation of Ser516. That COX-2 inhibition by aspirin resulted from the acetylation of Ser516 was confirmed by tryptic digestion and peptide mapping of COX-2 labeled with [1- 14C-acetyl]salicyclic acid. The efficacy of the sulfides in inhibiting COX- 2 activity in inflammatory cells, our recent results on the selectivity of 70 in attenuating growth of COX-2-expressing colon cancer cells, and its selectivity for inhibition of COX-2 over COX-1 in vivo indicate that this novel class of covalent modifiers may serve as potential therapeutic agents in inflammatory and proliferative disorders.
- Kalgutkar, Amit S.,Kozak, Kevin R.,Crews, Brenda C.,Hochgesang Jr., G. Phillip,Marnett, Lawrence J.
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p. 4800 - 4818
(2007/10/03)
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- A Novel Synthesis of (5Z,8Z,11Z,14Z,17Z)-5,8,11,14,17-Eicosapentaenoic Acid and Its Acetylenic Precursor
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A novel procedure of synthesis of (5Z,8Z,11Z,14Z,17Z)-5,8,11,14,17-eicosapentaenoic (timnodonic) acid and its acetylenic precursor, 5,8,11,14,17-eicosapentaynoic acid was developed.It uses polyacetylene strategy and a known reaction of cross-coupling between propargyl units and ω-acetylenes in the presence of copper(I) and sodium iodides and involves the in situ formation of organocopper compounds and propargyl iodides. - Key words: (5Z,8Z,11Z,14Z,17Z)-5,8,11,14,17-eicosapentaenoic acid; 5,8,11,14,17-eicosapentaynoic acid; polyacetylenic alcohols; cross-coupling
- Ivanov, I. V.,Groza, N. V.,Myagkova, G. I.
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p. 819 - 822
(2007/10/03)
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- Carbacyclins, process for the preparation thereof, and use thereof as medicinal agents
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The invention relates to carbacyclins of general Formula I STR1 wherein R1 is the residue CH2 OH or STR2 with R2 meaning a hydrogen atom, an alkyl, cycloalkyl, aryl residue, a STR3 or heterocyclic residue, or R1 is the residue STR4 with R3 meaning an alkanoyl or alkanesulfonyl residue of respectively 1-10 carbon atoms or the residue R2, or R1 is the residue STR5 wherein m is the number 1 or 2, X is an oxygen atom or a CH2 -group, A is a trans--CH=CH- or -- C--group, W is a free or functionally modified hydroxymethylene group wherein the OH-group can be in the α- or β- position, n is the number 1, 2, or 3, D is a straight-chain alkylene group of 1-5 carbon atoms, E is a --C C---bond or a --CR6 =CR7 --group wherein R6 and R7 are different from each other and mean a hydrogen atom or an alkyl group of 1-5 carbon atoms or a hydrogen atom or a halogen atom, preferably chlorine, R4 is an alkyl, cycloalkyl, or optionally substituted arly group, or a heterocyclic group, R5 is a free or functionally modified hydroxy group, and if R2 means a hydrogen atom, the salts thereof with physiologically compatible bases; to processes for the preparation thereof, and to the use thereof as blood-pressure-lowering agents.
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- ISOLATION AND TOTAL SYNTHESIS OF THE MAJOR CONSTITUENT OF THE ROOTS OF CENTAUREA INCANA: APLOTAXENE
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The major constituent of the petroleum ether extract of the root of Centaurea incana was identified as (8Z,11Z,14Z)-1,8,11,14-heptadecatetraene (Aplotaxene 1).A convergent and highly stereoselective synthesis of this compound is reported.
- Cossy, J.,Aclinou, P.
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p. 7615 - 7618
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF (9Z,15Z)-(11S,12S,13S)-11-HYDROXY-12,13-EPOXY OCTADECADIENOIC ACID: A CONSTITUENT OF RICE PLANT INFECTED WITH RICE BLAST DISEASE
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An elegant, stereoselective synthesis of (9Z,15Z)-(11S,12S,13S)-11-hydroxy-12,13-epoxy octadecadienoic acid (1) by enantioselective epoxidation is described.
- Rama Rao, A. V.,Radha Krishna, P.,Yadav, J.S.
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p. 1669 - 1670
(2007/10/02)
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- 2,5,6,7-tetranor-18,18,19,19-tetradehydro-4,8-inter-m-phenylene PGI2 derivatives
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Disclosed herein are novel prostaglandin I2 (PGI2) derivatives exhibiting excellent physiological activities, said derivatives being represented by the general formula: STR1 wherein R1, R2 and R3 are as defined herein.
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- 2,5,6,7-tetranor-4,8-inter-m-phenylene PGI2 derivatives
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Disclosed herein are novel prostaglandin I2 (PGI2) derivatives exhibiting excellent in vivo duration and activities, said derivatives being represented by the general formula: STR1 wherein R1, X, R2 and R3 are as defined herein.
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- Perfume compositions and perfumed products which contain one or more 4,7-alkadienals as the essential substance
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Perfume compositions and perfumed products containing as perfume component one or more 4,7-alkadienals with the formula STR1 wherein R represents a straight-chain or branched-chain alkyl or alkenyl group containing 2-5 carbon atoms and wherein the 4-5 double bond has the cis-configuration and the 7-8 double bond can have the cis or trans configuration.
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- PREPARATIVE SYNTHESIS OF TOSYLATES OF UNSATURATED ALCOHOLS AND UNSATURATED BROMIDES UNDER PHASE TRANSFER CONDITIONS
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A preparative synthetic method has been developed for tosylates of unsaturated alcohols and their conversion to bromides under phase transfer conditions in the case of alkyn-1-ols, E- and Z-alken-1-ols, 3-methyl-3-buten-1-ol and cyclopropylmethanol.
- Ishchenko, R. I..,Kovalev, B. G.,Khusid, A. Kh.
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p. 1076 - 1078
(2007/10/02)
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- A New Synthesis of Nona-2E,6Z-dienal
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Monosodio ethyl malonate on alkylation with 1-bromo-pent-2-yne (III) furnishes the diester (IV) which on decarbethoxylation with NaCl/DMSO, followed by LAH/EtOH reduction of the resultant ester (V), yields the carbinol (VI).Hydrogenation of VI in the presence of Lindlar's catalyst produces hept-4Z-en-1-ol (VII), which on pyridinium chlorochromate oxidation gives the aldehyde (VIII).Wittig-Horner reaction on VIII using ethyl diethylphosphonoacetate produces the dienoate (IX), which on LAH/EtOH reduction followed by oxidation with Corey's reagent, affords the title compound(I).
- Vig, O. P.,Sharma, M. L.,Gauba, Rita
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p. 313 - 314
(2007/10/02)
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- Volatile Flavor Components of Kogyoku Apples
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A steam distillate of Kogyoku apple juice was extracted with ethyl ether.The extract was separated into its acidic and neutral fractions, and the neutral fraction was further separated into five fractions by column chromatography.All these fractions were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry.Several compounds in the neutral fraction of the juice were isolated by preparative GC, and then identified by comparing their mass, infrared and nuclear magnetic resonance spectra with those of authentic compounds.Sixty-seven compounds were identified form the juice, 22 compounds being found for the first time as apple flavor components.Among them, the following compounds have not been previously reported as flavor components in any natural product; (Z)-5-octen-1-ol, (Z,Z)- and (E,Z)-3,5-octadien-1-ols, (Z,Z)- and (E,Z)-3,5-octadien-1-yl acetates, (Z)-5-octene-1,3-diol and 3-hydroxy-(Z)-5-octen-1-yl acetate.We also made a comparison of the volatile flavor compounds in the juice and peel of the same apples.
- Yajima, Izumi,Yanai, Tetsuya,Nakamura, Mikio,Sakakibara, Hidemasa,Hayashi, Kazuo
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p. 849 - 856
(2007/10/02)
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- Manufacture of 2-(alkyl, alkenyl or alkynyl) 3-carbalkoxyalkyl ketones from alpha, beta-unsaturated ketones
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The copper enolate of 3-allylcyclopentanone is alkylated with an alkyne so as to form the 2-alkynyl, 3-allylcyclopentanone which is then subjected to ozonolysis and oxidative cleavage to form 2-alkynylcyclopentan-3-one-1-yl alkylcarboxlic acid. The acid can be esterified to form a 2-alkynyl-3-carbalkoxyalkyl ketone which, in turn, can be hydrogenated to convert the alkynyl moiety to alkenyl or alkyl moieties. The procedure is particularly useful in the synthesis of methyl dl-jasmonate, dehydrojasminate and dihydrojasmonate.
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