- Improved synthesis of (Z,E)-9,11,13-tetradecatrienal, the sex pheromone of the Carob Moth Apomyelois (=Ectomyelois) ceratoniae (Lepidoptera: Pyralidae)
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(Z,E)-9,11,13-Tetradecatrienal is a sex pheromone component emitted by virgin females of the Carob Moth Apomyelois ceratoniae Zeller (Lepidoptera: Pyralidae) which is an important pest of Iranian pomegranate fruits. Chemical control of this pest is not possible and biological methods with pheromones are used. The synthesis of the major component of the sex pheromone was achieved in fewer steps and with lower cost than previously. (Z,E)-9,11,13-Tetradecatrienal was synthesised by four steps with 59% overall yield. The coupling of a conjugated dienynol intermediate from E-1,2-dichloroethylene with vinyl magnesium bromide was achieved in good yield and followed by reduction of dienynol with activated zinc in THF-H2O and oxidation gave the aldehyde of the sex pheromone.
- Noorbakhsh, Saeede,Alizadeh, Babak Heidary,Saber, Moosa,Farazmand, Hossein
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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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- Structure based interference with insect behaviour - Cyclopropene analogues of pheromones containing Z-alkenes
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Analogues of the pheromones of three insect species (Musca domestica L., Plutella xylostella L. and Ephestia elutella Hbn.) in which a Z-alkene has been replaced by a 1,2-disubstituted cyclopropene have been synthesized. The analogues interfere with normal mating behaviour for each species.
- Al Dulayymi, Juma'a R.,Baird, Mark S.,Simpson, Michael J.,Nyman, Susan,Port, Gordon R.
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- The first stereoselective synthesis of a dithiane derivative of the C18 β-diketodiene system proposed for an active compound isolated from Cantharellus cibarius (chanterelle)
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A stereocontrolled synthesis of a thioketal system that is a direct precursor of an active compound isolated from chanterelle was accomplished by using readily available methyl 11-[2-(2-oxoethyl)-1,3-dithian-2-yl]undec-9-ynoate as a key intermediate. The synthesis involves simple and straightforward reactions, such as addition of a lithiated alkyne to an aldehyde, alkyne hydrogenation using nickel boride, alcohol oxidation with Dess-Martin periodinane, and Z-to-E enone isomerization.
- Grodner, Jacek,Golebiewski, W. Marek,Willis, Michael C.,Osborne, James D.,Gucma, Miros?aw
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- Synthesis of dansyl-labeled probe of thiophene analogue of annonaceous acetogenins for visualization of cell distribution and growth inhibitory activity toward human cancer cell lines
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The convergent synthesis of the dansyl-labeled probe of the thiophene-3-carboxamide analogue of annonaceous acetogenins, which shows potent antitumor activity, was accomplished by two asymmetric alkynylations of the 2,5-diformyl THF equivalent with an alkyne having a thiophene moiety and another alkyne tagged with a dansyl group. The growth inhibitory profiles toward 39 human cancer cell lines revealed that the probe retained the biological function of its mother compound, and would be useful for studying cellular activity.
- Kojima, Naoto,Suga, Yuki,Matsumoto, Takuya,Tanaka, Tetsuaki,Akatsuka, Akinobu,Yamori, Takao,Dan, Shingo,Iwasaki, Hiroki,Yamashita, Masayuki
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- Synthesis of the (17R)- and (17S)-isomers of volicitin, an elicitor of plant volatiles contained in the oral secretion of the beet armyworm
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Both the (17R)- and (17S)-isomers of volicitin, which is contained in the oral secretion of the beet armyworm and induces corn seedlings to emit a blend of volatile compounds to attract the natural enemy of the herbivore, were synthesized via the semi-hyd
- Itoh, Seiji,Kuwahara, Shigefumi,Hasegawa, Morifumi,Kodama, Osamu
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- The synthesis and biological evaluation of a kabiramide C fragment modified with a WH2 consensus actin-binding motif as a potential disruptor of the actin cytoskeleton
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The F-actin depolymerisation potency of a fragment of kabiramide C was increased when modified with a WH2 consensus actin-binding motif LKKV. Despite its low affinity for actin monomers, a shorter analogous fragment not bearing LKKV was identified as a potent inhibitor of actin polymerisation and a promoter of its depolymerisation, resulting in a loss of actin stress fibres in cells.
- Tetlow, Daniel J.,Winder, Steve J.,A?ssa, Christophe
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- Partially fluorinated analogs of (Z)-9-dodecenyl acetate: Probes for pheromone hydrophobiclty requirements
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Allylic difluoromethylene, terminal trifluoromethyl, and pentafluoroethyl analogs of (Z)-9-dodecenyl acetate were synthesized to probe the requirements for hydrophobicity of the alkyl terminus in pheromone activity. These compounds show unexpected and varied behavioral activities in assays using the European grape berry moth.
- Sun, Wei-Chuan,Prestwich, Glenn D.
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- Tetris in monolayers: Patterned self-assembly using side chain shape
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The "kinked" shapes of conjugated alkadiynes constrain chain packing in monolayers on HOPG. Centrally located diyne units permit assembly of 1,5-bis(alkadiyne)anthracene monolayers. Off-center diynes inhibit self-assembly. Shape matched pairs of off-center diyne chains direct self-assembly of compositionally patterned, two component monolayers.
- Xue, Yi,Zimmt, Matthew B.
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- Stereodirectional synthesis of the main component of pheromone (9Z,12E)-tetradeca-9,12-dienyl acetate by cross-coupling
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By cross-coupling of alkynyl cuprate with crotyl halides was synthesized (9Z,12E)-tetradeca-9-12-dienyl acetate, the main component of pheromones of several insect species Lepidoptera. The assignment of the chemical shifts of diene system was performed by 1H and 13NMR spectroscopy.
- Matveeva,Erin,Leshcheva,Kurts
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- Highly fluorinated C18 fatty acids: Synthesis and interfacial properties
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A fluorinated oleic acid 1-Z containing a perfluorooctyl group and its analogues (E-isomer 1-E, alkyne type 2 and saturated type 3) were synthesized in good yields. In these syntheses, it was found that a key compound 5 could be converted to each of 1-Z, 1-E and 2. Furthermore, equilibrium spreading pressures of their monolayers at the air-water interface were measured in order to demonstrate how the degree of unsaturation in the hydrophobic chain, the geometric isomerization, and the presence of F-atoms influence the monolayer stability. Irrespective of the structural alteration in the hydrophobic chains, the fluorinated fatty acids formed more stable monolayers with high spreading pressures as compared to their hydrocarbon counterparts.
- Takai, Katsuki,Takagi, Toshiyuki,Baba, Teruhiko,Kanamori, Toshiyuki
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- Preparation method of furan macrocyclic compound, prepared furan macrocyclic compound and application of furan macrocyclic compound
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The invention discloses a preparation method of a furan macrocyclic compound, the prepared furan macrocyclic compound and application of the furan macrocyclic compound. According to the preparation method disclosed by the invention, a macrocyclic alkyne olefine aldehyde compound is used as a raw material and is subjected to cyclization reaction under the catalysis of metal. The preparation method disclosed by the invention is simple to operate, simple and convenient in steps and high in efficiency, and the atom utilization rate is up to 100%. The reaction raw material macrocyclic alkyne olefine aldehyde compound can be obtained by a cyclic ketone compound or an alkyl alcohol compound through several steps of reaction with mature process and very high efficiency. The furan macrocyclic compound with a brand-new and special structure is obtained by the method, can be used as an element unit to synthesize a series of oligomerization furan compounds, and has potential optical application value.
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Paragraph 0174-0175; 0179
(2021/08/07)
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- Oxidative Deprotection of p-Methoxybenzyl Ethers via Metal-Free Photoredox Catalysis
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An efficient and greener deprotection method for p-methoxybenzyl (PMB) ethers using a metal-free visible light photoredox catalyst and air and ammonium persulfate as the terminal oxidants is presented. Various functional groups and protecting groups were tolerated in the developed method to achieve good to excellent yields in short reaction times. Significantly, the developed method was compatible with PMB ethers derived from primary, secondary, and tertiary alcohols and a gram-scale reaction. Mechanistic studies support a proposed reaction mechanism that involves single electron oxidation of the PMB ether.
- Ahn, Deok Kyun,Kang, Young Woo,Woo, Sang Kook
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p. 3612 - 3623
(2019/03/11)
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- Enantioselective Rhodium-Catalyzed Dimerization of ω-Allenyl Carboxylic Acids: Straightforward Synthesis of C2-Symmetric Macrodiolides
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Herein, we report on the first enantioselective and atom-efficient catalytic one-step dimerization method to selectively transform ω-allenyl carboxylic acids into C2-symmetric 14- to 28-membered bismacrolactones (macrodiolides). This convenient asymmetric access serves as an attractive route towards multiple naturally occuring homodimeric macrocyclic scaffolds and demonstrates excellent efficiency to construct the complex, symmetric core structures. By utilizing a rhodium catalyst with a modified chiral cyclopentylidene-diop ligand, the desired diolides were obtained in good to high yields, high diastereoselectivity, and excellent enantioselectivity.
- Steib, Philip,Breit, Bernhard
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p. 6572 - 6576
(2018/05/08)
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- Identification of Novel Triazole-Based Nicotinamide Phosphoribosyltransferase (NAMPT) Inhibitors Endowed with Antiproliferative and Antiinflammatory Activity
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Nicotinamide phosphoribosyltransferase (NAMPT) is a key enzyme involved in the recycling of nicotinamide to maintain adequate NAD levels inside the cells. It has been postulated to be a pharmacological target, as it is overexpressed in cancer cells as well as in inflammatory diseases. We describe the synthesis and characterization of a novel class of one-digit nanomolar NAMPT inhibitors based on in vitro characterization. The most active compound tested, 30c, displayed activity in xenograft and allograft models, strengthening the potential of NAMPT inhibitors as antitumoral drugs. Furthermore, in the present contribution we describe the ability of 30c to significantly improve the outcome of colitis in mice. Given that this is the first report of an effect of NAMPT inhibitors in colitis, this result paves the way for novel applications for this class of compounds.
- Travelli, Cristina,Aprile, Silvio,Rahimian, Reza,Grolla, Ambra A.,Rogati, Federica,Bertolotti, Mattia,Malagnino, Floriana,Di Paola, Rosanna,Impellizzeri, Daniela,Fusco, Roberta,Mercalli, Valentina,Massarotti, Alberto,Stortini, Giorgio,Terrazzino, Salvatore,Del Grosso, Erika,Fakhfouri, Gohar,Troiani, Maria Pia,Alisi, Maria Alessandra,Grosa, Giorgio,Sorba, Giovanni,Canonico, Pier Luigi,Orsomando, Giuseppe,Cuzzocrea, Salvatore,Genazzani, Armando A.,Galli, Ubaldina,Tron, Gian Cesare
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p. 1768 - 1792
(2017/03/17)
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- Identification of a novel NAMPT inhibitor by combinatorial click chemistry and chemical refinement
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The identification of compounds able to inhibit the NAD salvage pathway is experiencing a growing popularity as it has been proposed to be a novel target for antitumoral and anti-inflammatory drugs. In this manuscript, we used the copper-catalyzed [3+2] cycloaddition between azides and alkynes (click chemistry) to identify novel NAMPT inhibitors with a triazole-containing tail group. 720 compounds were synthesized in the first round, allowing the identification of 17 hit compounds. The second round of optimization brought about the discovery of compound 43 which displayed a cytotoxicity of 20 nM on neuroblastoma cancer cells and an inhibition of NAMPT of 114 nM.
- Theeramunkong,Galli,Grolla,Caldarelli,Travelli,Massarotti,Troiani,Alisi,Orsomando,Genazzani,Tron
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p. 1891 - 1897
(2015/10/20)
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- A one-pot allylation-hydrostannation sequence with recycling of the intermediate tin waste
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A one-pot allylation and hydrostannation of alkynals where the tin byproduct formed in the first step of the reaction is recycled and used in the second step of the sequence is presented. Specifically, a BF3· OEt2-promoted allylstannation of the aldehyde moiety in the alkynal is followed by the introduction of polymethylhydrosiloxane (PMHS) and catalytic B(C6F5)3, which convert the tin byproduct of the allylation into Bu3SnH, which then hydrostannates the alkyne in the molecule. 119Sn and 11B NMR data suggest an organotin fluoride species is formed during the allylation step and involved in the tin recycling step.
- Ghosh, Banibrata,Amado-Sierra, Maria Del Rosario I.,Holmes, Daniel,Maleczka, Robert E.
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supporting information
p. 2318 - 2321
(2014/05/20)
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- In situ proteome profiling of C75, a covalent bioactive compound with potential anticancer activities
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A library of cell-permeable, minimally tagged C75 analogues was synthesized and used to uncover biological targets in human liver cancer cells. Known targets of C75, namely FASN and CPT1A, together with other unknown targets, including PDIA3, TFRC, and GAPDH, were thus identified.
- Cheng, Xiamin,Li, Lin,Uttamchandani, Mahesh,Yao, Shao Q.
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p. 1414 - 1417
(2014/04/03)
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- Maltoside and Phosphocholine Derivatives, Uses thereof and Methods of Preparing Artificial Lipid Structures Thereof
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Disclosed are saccharide and phosphocholine derivatives. The derivatives include azide and alkyne derivatives which form one end of a variable length carbon chain. The opposite end of the variable length carbon chain is covalently linked to the saccharide or phosphocholine. The saccharide may be, for instance, a maltoside. The alkyne and azide derivatives of the saccharides and phosphocholine may be reacted together to form amphiphilic molecules useful in cellular membrane studies and applications. By adjusting the length of the carbon chain, the biochemical and biophysical properties of the resultant 1,4-disubstituted 1,2,3-triazole compounds may be custom tailored for the intended application. Resultant molecules may form micelles, bicelle, lipid bilayers and other like structures useful in the isolation and purification of membrane bound or membrane associated proteins and biochemical components. The saccharides and phosphocholine molecules may be alternatively substituted as desired to provide additional flexibility in designing the desired end product.
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Paragraph 0056
(2013/04/24)
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- Site-specific 2H-labeled oleic acid and derived esters for use as tracers of ethyl oleate metabolism in honey bees
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The inventory of labeled fatty acids and protocols for their syntheses are constantly increasing, but site-specific labeled precursors in biosynthetic studies are still needed. Ethyl oleate (EO) is an important primer pheromone in honeybees, which is responsible for the regulation of behavioral maturation. During our biosynthetic studies on EO, a site-specific labeled oleic acid precursor was required. In this report, a synthetic route adaptable to the preparation of [9,10,11,11-D4] oleic acid and its derived esters for use as tracers of EO metabolism in honey bees is presented. Copyright
- Chen, Hao,Plettner, Erika
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scheme or table
p. 66 - 70
(2012/06/30)
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- Investigating inner-sphere reorganization via secondary kinetic isotope effects in the C-H cleavage reaction catalyzed by soybean lipoxygenase: Tunneling in the substrate backbone as well as the transferred hydrogen
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This work describes the application of NMR to the measurement of secondary deuterium (2° 2H) and carbon-13 (13C) kinetic isotope effects (KIEs) at positions 9-13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using LA labeled with either protium (11,11- h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° 2H and 13C KIEs on kcat/Km directly for 11,11-d2-LA, whereas the values for the 2° 2H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° 2H and 13C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of nonclassical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 1981, 85, 3763] to model the inner-sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° 2H KIEs.
- Meyer, Matthew P.,Klinman, Judith P.
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supporting information; experimental part
p. 430 - 439
(2011/04/16)
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- Design, synthesis, and self-assembly of an ether and amide linkage-based cyclic lipid
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A novel 48-membered cyclic lipid, in which two ether and two amide groups serve as a linker between its hydrophilic and hydrophobic moiety, was synthesized starting from d-1,2-O-isopropylidene-sn-glycerol. The synthetic scheme is featured by the selective
- Shibakami, Motonari,Miyoshi, Shin,Nakamura, Makoto,Goto, Rie
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body text
p. 2651 - 2654
(2010/01/07)
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- Synthesis of linoleic acids combinatorially labeled at the vinylic positions as substrates for lipoxygenases
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Mammalian lipoxygenases have been implicated in a number of inflammation-related human diseases. Soybean lipoxygenase-1 is the archetypical example of known lipoxygenases. Here we report the synthesis of linoleic acid and (11,11)-d2-linoleic acid which are combinatorially labeled at the vinylic positions (9, 10, 12, and 13). Combinatorial labeling schemes allow for the simultaneous determination of KIEs in enzymatic reactions using NMR. Substrates are, thus, available as probes of detailed mechanism in kinetic isotope effect (KIE) studies of lipoxygenases.
- Meyer, Matthew P.,Klinman, Judith P.
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p. 3600 - 3603
(2008/09/19)
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- Synthesis of photoactivatable analogues of lysophosphatidic acid and covalent labeling of plasma proteins
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Lysophosphatidic acids hearing a benzophenone group in either the sn-1 or sn-2 chain of an oleoyl-type ester or oleyl-type ether chain and 32P in the phosphate group were synthesized. The benzophenone moiety was introduced by selective hydrobor
- Li, Zaiguo,Baker, Daniel L.,Tigyi, Gabor,Bittman, Robert
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p. 629 - 635
(2007/10/03)
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- Preparation of deuterium-labeled monounsaturated and saturated fatty acids for use as stable isotope metabolic tracers
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Synthetic routes adaptable to the preparation of a variety of d 7-labeled mono-unsaturated and saturated fatty acids are reported. Using these reaction sequences, d7-oleic [18:1 (9c)], d 7-elaidic [18:1 (9t)], and d7-stearic acid (18:0) were prepared for use in metabolism studies as stable isotope-labeled tracers. Copyright
- Crane, Sheldon N.,Bateman, Kevin,Gagne, Sebastien,Levesque, Jean-Francois
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p. 1273 - 1285
(2007/10/03)
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- Synthesis of polyacetylenic acids isolated from Nanodea muscosa
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The first total synthesis of two linear polyacetylenic compounds is described. The synthesis of (E)-octadec-13-en-11-ynoic acid 1 and (E)-octadec-13-en-9,11-diynoic acid 2 by using the vinylic telluride coupling reaction was accomplished.
- Alves, Diego,Nogueira, Cristina W.,Zeni, Gilson
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p. 8761 - 8764
(2007/10/03)
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- First total synthesis of natural aplyolides B and D, ichthyotoxic macrolides isolated from the skin of the marine mollusk Aplysia depilans
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A convergent pathway is described for the synthesis of the marine macrolides aplyolides B (2) and D (3). Stereoselective preparation of a key fragment was achieved by Sharpless asymmetric dihydroxylation of eneyne 10.
- Spinella, Aldo,Caruso, Tonino,Coluccini, Carmine
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p. 1681 - 1683
(2007/10/03)
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- Synthesis of cyclo-1,3-dien-5-ynes
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Cyclo-1,3-dien-5-ynes with ring sizes from 10 to 14 (6a-e) have been prepared for the first time by using a five-step synthesis starting from the alkynols 7a-e. The final ring-closure was achieved by McMurry coupling of the α,ω-dialdehydes 12a-e with the complex TiCl3(DME)1.5. Thermal isomerization of the cyclodienynes leads to the corresponding benzocycloalkenes, and it has been shown that the ring size has a considerable influence on the temperature necessary for thermocylization.
- Hopf, Henning,Krueger, Anke
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p. 4378 - 4385
(2007/10/03)
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- A versatile approach to the synthesis of 9(Z)-unsaturated acyclic insect pheromones from undec-10-enoic acid
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A general approach to the synthesis of 9(Z)-unsaturated acyclic insect pheromones from undec-10-enoic acid was developed. The method comprises the conversion of the acid into undec-10-enyl acetate, shortening of its carbon chain to afford dec-9-enyl acetate (via 11-acetoxyundecanoic acid), and a two-step transformation of the latter into the key intermediate, dec-9-yn-1-ol, by sequential bromination - dehydrobromination. The elimination of two HBr molecules from the dibromide is effectively performed using Bu1OK in the presence of dibenzo-18-crown-6 as the catalyst.
- Ishmuratov,Kharisov,Yakovleva,Botsman,Galeeva,Ishmuratova,Tolstikov
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p. 1595 - 1597
(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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- Stereoselective synthesis of (S)-13-hydroxy octadeca-(9Z, 11E)-di- and (9Z, 11E, 15Z)-trienoic acids: Selfdefensive substances against rice blast disease
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A highly stereoselective synthesis of [(S)-coriolic acid] (1) and first total synthesis of (S)-15,16-didehydrocoriolic acid (2) by a Pd°-CuI catalysed coupling of (S )-halovinylalcohol with acetylenic moiety is described. The required optically pure chlor
- Yadav,Deshpande,Sharma
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p. 4465 - 4474
(2007/10/02)
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- Synthesis of 9Z,11E,13-Tetradecatrienal, the Major Component of the Sex Pheromone of the Carob Moth, Ectomyelois ceratoniae (Lepidoptera: Pyralidae)
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9Z,11E,13-Tetradecatrienal, a component of the sex pheromone of the carob moth, was synthesized by a short and efficient route, with a high degree of stereoselectivity.Key steps included the Pd-catalyzed construction of a conjugted dienynol intermediate f
- Millar, Jocelyn G.
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p. 2473 - 2476
(2007/10/02)
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- A facile synthesis of cotton bollworm (Heliothis armigera) pheromone components: (Z)-11-Hexadecenal and (Z)-9-hexadecenal
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(Z)-Hexadecenal (1) and (Z)-9-hexadecenal (2) have been synthesised starting from easily accessible propargyl alcohol.Alkylation of propargyl alcohol yields 3 and 4, which on acetylene-zipper reaction give terminal acetylenes (5 and 6, R'=H).Alkylation of 5 and 6 followed by depyranylation afford 7 and 8.Partial cis-hydrogenation of these with P2Ni followed by PCC oxidation give compounds 1 and 2.
- Mithran, S.,Mamdapur, V. R.
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p. 755 - 756
(2007/10/02)
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- Synthesis of all-trans-Parinaric Acid-d8 Specifically Deuterated at All Vinyl Positions
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Parinaric acid is a widely used fluorescent probe of biological systems.The all-trans isomer (9(E),11(E),13(E),15(E)-octadecatetraenoic acid) specifically deuteriated at all vinyl positions was prepared by using the Wittig reaction to couple a diene phosphorane with an α,β-unsaturated aldehyde-ester.The preparation of each component included the stereoselective reduction of a substituted propynoic ester with lithium aluminum deuteride (LAD), introducing the trans double bond as well as most of the deuterium in one step, in high isotopic purity without unwanted hydrogen-deuterium exchange.By inclusion of deuterium, the probe can be used with other techniques, such as deuterium NMR and neutron diffraction, further increasing its utility.The synthesis can be used to prepare other tetraenes by correct choice of starting propynoic esters.
- Goerger, Michael M.,Hudson, Bruce S.
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p. 3148 - 3153
(2007/10/02)
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- SYNTHESIS AND PHISIOLOGICAL ACTIVITIES OF BOTH ENANTIOMERS OF CORIOLIC ACID AND THEIR GEOMETRIC ISOMERS
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Both enantiomers of coriolic acid and their geometric isomers are synthesized highly selectively.These acids are found to exhibit similar inhibition activity toward spore germination of rice blast fungus.
- Kobayashi, Yuichi,Okamoto, Sentaro,Shimazaki, Toshiyuki,Ochiai, Yoshinori,Sato, Fumie
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p. 3959 - 3962
(2007/10/02)
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- New Synthesis of Macrolide Pheromones of the Flat Grain Beetle, Cryptolestes pusillus Schoenherr
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(Z)-3-Dodecan-12-olide 1 and (5Z,13S)-5-tetradecen-13-olide 2, the macrolide pheromones of the flat grain beetle, were synthesized by employing the acetylene zipper reaction in the key steps.
- Sakai, Teruyuki,Hamamoto, Hiroshi,Mori, Kenji
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p. 1621 - 1628
(2007/10/02)
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- PEPARATION OF (Z) and (E)-9-DODECENYL ACETATES
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The sexual pheromones (Z)-9-dodecenyl acetate (IXa) and (E)-9-dodecenyl acetate (IXb) were synthesized using facile preparation of the acetylenic precursor 9-decyn-1-ol (IV), from tetrahydrofurfuryl chloride (I).Hydroxyl groups of intermediates in the subseqent steps were protected by the ethoxyethyl group.
- Koerblova, Eva,Romanuk, Miroslav
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p. 2284 - 2288
(2007/10/02)
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- A STEREOSELECTIVE SYNTHESIS OF CORIOLIC ACID AND DIMORPHECOLIC ACID
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Described herein is a convenient synthesis of coriolic acid (1) and dimorphecolic acid (2), the two natural ionophores derived respectively from bovine heart mitochondria and also shown to be self defensive substances in rice plant against rice blast disease.
- Rao, A. V. Rama,Reddy, E. Rajarathnam,Sharma, G. V. M.,Yadagiri, P.,Yadav, J. S.
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p. 465 - 468
(2007/10/02)
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- Kinetic study of deuterium-labelled polyenephosphatidylcholine after oral administration to rats
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Deuterium-labelled di-([15,15,16,16-2H4]-linoleoyl)-3-sn-glycerophosphocholine was used as a tracer of the major component of soybean polyene-3-sn-phosphatidylcholine to study the pharmacokinetics of a natural product after oral administration to rats. For this purpose a method was developed to isolate the phosphatidylcholine fraction from blood in a highly purified form. Only 200 pg deuterium-labelled fatty acid generated from the phosphatidylcholine fraction and a ratio of one molecule of deuterium-labelled stearic acid to 500 molecules of stearic acid are necessary for a reproducible measurement by gas chromatography/mass spectrometry. The highest amount of di-([15,15,16,16-2H4]-linoleoyl)-3-sn-glycerophosphocholine (0.12% dose/ml, i.e. 2.1% of the maximum absorbed dose) was detected in blood 6 h after administration. The results are comparable with those found after administration of di-[1-14C]-linoleoyl-3-sn-glycero-phosphocholine. Hence it is possible to use deuterium-labelled polyenephosphatidylcholine instead of radioactively labelled polyenephosphatidylcholine, especially if a harmless tracer is required.
- Brekle,Zierenberg
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p. 130 - 132
(2007/10/02)
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- Metamorphosis of Castor Oil to Insect Sex-pheromones and Useful Synthons
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The primary fragmentation products of Castor oil (1), namely, methyl undec-10-enoate (2) and sebacic acid (3) have been converted, using novel reactions and strategies into synthons of the type H-CC-(CH2)n-3-CH2OTHP (n=6=4; n=7=14; n=8=22; n=9=29).A surprisingly clean decarboxylative elimination of sebacic acid monoester gives methyl non-8-enoate (7), a synthon related to recefeiolide and a precursor to 4, the utility of which, has been illustrated with the synthesis of insect-pheromones of the species Grapholita molesta.Methyl dec-9-enoate (15) has been prepared by a novel and practical terminal ? to lower terminal ? degradation of 2.Compound 7 has been transformed via synthon 14 to the insect sex-pheromones of the species, Spodoptera frugiperda, Heliothis virescens and Paralobesia viteana in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxyundec-10-yne (22) readily prepared from 2, has been used to illustrate a new strategy in pheromone synthesis, namely, the use of coupling elements, leading to the preparation of bombykol in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxydodec-11-yne (29), already reported, has been transformed to vaccenic acid (30), the transposed ?-isomer of oleic acid, in good yields, thus demonstrating the use of acetylide synthons for the preparation of rare fatty acids also.
- Ranganathan, S.,Maniktala, Vibha,Kumar, Raaj,Singh, G. P.
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p. 1197 - 1207
(2007/10/02)
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- Acides gras marques en position ω par un nucleide radioactif emetteur γ
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The synthesis of many saturated, acetylenic, olefinic (Z or E) fatty acids labeled with 123I or 131I at the ω-position has been achieved.The radioactive iodine atom is introduced by a I-, *I- exchange reaction; the influence on the yield of several parameters - presence of iodine carrier, fatty acid and water concentrations, solution acidity - has been studied.Experimental conditions which produce labeling yields higher than 95percent have been defined; these results have lead to a very easy labeling method used in several hospitals in the external study of myocardial metabolism of fatty acids.
- Riche, Francoise,Mathieu, Jean-Paul,Vincens, Maurice,Bardy, Andre,Comet, Michel,Vidal, Michel
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- Synthesis of ω-Tritiated and ω-Fluorinated Analogues of the Trail Pheromone of Subterranean Termites
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A series of unsaturated ω-fluoro alcohols have been prepared stereoselectively.These simple compounds are structural analogues of the trail pheromone of termites in the genus Reticulitermes.The toxicity of these ω-fluoro alcohols to R. flavipes is maximal for the C12 alcohols, and the attractiveness of these C12 analogues increases in the order saturated alkanol -12-fluoro alcohols and a -nonfluorinated analogue were prepared to examine the catabolism of the pheromone analogues.
- Carvalho, Joan F.,Prestwich, Glenn D.
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p. 1251 - 1258
(2007/10/02)
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- Alkyne isomerization reagents: mixed alkali metal amides
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Addition of sodium and potassium alkoxides, particularly potassium tert-butoxide, to the lithium salts of either 1,2-diaminoethane or 1,3-diaminopropane afford alkyne isomerization reagents that effect triple bond migration to the end of a methylene chain under milder conditions and in higher yield than do previously reported reagents.
- Abrams, Suzanne R.
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p. 1333 - 1334
(2007/10/02)
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- Some alkali metal alkyl amides as alkyne isomerization reagents : selective isomerization of one triple bond of a diynol
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The lithium and sodium salts of 1,2-diaminoethane, 1,3-diaminopropane, n-butylamine, and the lithium salt of isobutylamine were studied as potential reagents for isomerzation of triple bonds in alkyn-1-ols.The sodium salts of the diamines afforded high yields of the ω-alkyn-1-ol.Somewhat surprisingly, the sodium salt of n-butylamine also effects isomerization to the terminal position.The lithium salt of 1,3-diaminopropane gave the highest conversion of 2- to 3-alkyn-1-ol.A novel, selective rearrangement of one triple bond of a diynol, a 2,ω- to 3,ω-diyn-1-ol isomerization, was incorporated into a synthesis of the insect sex pheromone 3,13-octadecadienol acetate.
- Abrams, Suzanne R.,Nucciarone, Donaato D.,Steck, Warren F.
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p. 1073 - 1076
(2007/10/02)
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- The rearrangement of isomeric linear decyn-1-ols by reaction with the sodium salt of 1,3-diaminopropane
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Isomerization of straight chain decyn-1-ols mediated by the sodium salt of 1,3-diaminopropane was studied as a function of time, temperature, and the initial position of the triple bond.At 50 deg C 9-decyn-1-ol, the thermodynamically favoured isomer, was formed rapidly regardless of the initial position of the triple bond.At lower temperatures the appearance of intermediate isomers was observed.The homopropargylic isomer was found to be remarkably stable, and under suitable conditions, conversion of 2- to 3-decyn-1-ol was carried out in 68 percent isolated yield.
- Macaulay, Suzanne R.
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p. 2567 - 2572
(2007/10/02)
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