- Synthesis and Properties of Aromatic-Terminated Diacetylene Organogelators and Their Application to Photopatterning of Polydiacetylenes
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A series of simply structured diacetylene-diamide-based gelators (DAGs) with aromatic terminals were synthesized, and their gelation and subsequent photopolymerization abilities were analyzed. DAGs with an adequate spacer length (n) and tolyl terminals (DA-Tn) interacted with aromatic solvents, such as benzene and xylenes, at elevated temperatures. During the subsequent cooling process, the DAGs interacted with each other through CH-πinteractions at their terminal positions. They also formed one-dimensional hydrogen bonding arrays through secondary amides, leading to stable organogels. These gels polymerized into π-conjugated polydiacetylenes (PDAs) under ultraviolet irradiation. In the p-xylene gels of DA-Tn, the spacer length exerted characteristic odd-even effects on the photopolymerization rates over a certain range (n = 3-6), which can be explained by periodic changes in the uniformity of the molecular packing modes. When the gelling solvent was changed to cyclohexane, the gelation and photopolymerization abilities were greatly improved because the DA-Tn gel networks became highly crystallized and transparent to ultraviolet light (254 nm). The ultimate conversion to PDA from DA-T8/cyclohexane gels was 45.2 wt %. Applying photolithographic techniques to the DAG with excellent photopolymerizability in the film state, we successfully fabricated microscale photopatterns of PDA. We also established a convenient removal process (development process) of DA monomers in unexposed areas. The resulting PDA patterns were quite stable to ambient light stimuli.
- Aoki, Ken'Ichi,Horitsugu, Kousuke,Narazaki, Kenta,Seki, Atsushi,Takahashi, Daiki,Tamaoki, Nobuyuki
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p. 13160 - 13169
(2021/11/16)
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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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- INSULIN CONJUGATES
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The present invention relates to a conjugate comprising a sulfonamide of formula (I) and an active pharmaceutical ingredient such as an insulin analog comprising at least one mutation relative to the parent insulin, wherein the insulin analog comprises a mutation at position B16 which is substituted with a hydrophobic amino acid and/or a mutation at position B25 which is substituted with a hydrophobic amino acid. The present invention further relates to a sulfonamide of formula (A). Moreover, the present invention relates to an insulin analog comprising at least one mutation relative to the parent insulin.
- -
-
Paragraph 0580; 0592-0595
(2020/07/05)
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- Synergistic Gold and Copper Dual Catalysis for Intramolecular Glaser–Hay Coupling: Rapid Total Synthesis of Ivorenolide B
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A synergistic dual catalysis approach involving gold and copper catalysts for the synthesis of macrolactones bearing 1,3-butadiynes through an intramolecular Glaser–Hay coupling reaction in good yield is described. This dual catalytic system exhibited good selectivity, reactivity and functional group tolerance. This unique process offers a paradigm shift: the potential as well as the versatility of this novel method is not only exemplified for the synthesis of macrolactones of different ring size but also for the rapid total synthesis of ivorenolide B, a new class of macrolides endowed with conjugated 1,3-diyne motif, having impressive immunosuppressive activities.
- Rangaraju, Sudheer K.,Gonela, Uma Maheshwar,Kavita, Aala,Yadav, Jhillu S.,Mohapatra, Debendra K.
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supporting information
p. 4376 - 4380
(2018/09/11)
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- Succinct synthesis of saturated hydroxy fatty acids and: In vitro evaluation of all hydroxylauric acids on FFA1, FFA4 and GPR84
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Saturated hydroxy fatty acids make up a class of underexplored lipids with potentially interesting biological activities. We report a succinct and general synthetic route to saturated hydroxy fatty acids hydroxylated at position 6 or higher, and exemplify this with the synthesis of hydroxylauric acids. All regioisomers of hydroxylauric acids were tested on free fatty acid receptors FFA1, FFA4 and GPR84. The results show that the introduction of a hydroxy group and its position have a high impact on receptor activity.
- Kaspersen, Mads Holmgaard,Jenkins, Laura,Dunlop, Julia,Milligan, Graeme,Ulven, Trond
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p. 1360 - 1365
(2017/07/07)
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- Methods and compositions for protein labeling using lipoic acid ligases
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The present disclosure provides compositions and methods of use thereof for labeling peptide and proteins in vitro or in vivo. The methods described herein employ lipoic acid ligase or mutants thereof, and lipoic acid analogs (e.g., lipoic acid analogs comprising a resorufin moiety) recognized by lipoic acid ligase and lipoic acid ligase mutants. Also provided herein is a method of imaging protein-protein interaction via a reaction mediated by lipoic acid ligase.
- -
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Page/Page column 35; 36
(2016/04/05)
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- Configurational Assignment of ‘Cryptochiral’ 10-Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis
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An asymmetric catalytic total synthesis of (S)-10-hydroxystearic acid (1) for comparison of its absolute configuration to that of samples obtained by fermentative hydration of oleic acid is reported. The synthesis involves two catalytic key-steps, namely Ru-catalyzed anti-Markovnikov hydration of 9-decynoic acid (7) to 10-oxodecanoic acid (5), followed by titanium-mediated asymmetric catalytic addition of dioctylzinc (25) to 5 in presence of the chiral ligand N,N’-((1R,2R)-cyclohexane-1,2-diyl)bis(1,1,1-trifluoromethanesulfonamide) (6). The synthesis is short and efficient and avoids use of protecting groups. Ozonolysis of 10-undecynoic acid (9) to 5 provides an alternative entry point into the synthetic route. The double dehydrobromination of (ω,ω-1)-dibromoalkanoic acids to ω-alkynoic acids under a variety of conditions was investigated with 10,11-dibromoundecanoic acid (11) as model substrate and using qNMR to quantify all reaction products. The synthetic approaches presented here have the potential to be generalized to the asymmetric catalytic synthesis of a variety of n-hydroxy-fatty acids.
- Brunner, Andreas,Hintermann, Lukas
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p. 928 - 943
(2016/12/09)
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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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p. 1181 - 1189
(2015/04/14)
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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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- Design and synthesis of protein kinase C epsilon selective diacylglycerol lactones (DAG-lactones)
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DAG-lactones afford a synthetically accessible, high affinity platform for probing structure activity relationships at the C1 regulatory domain of protein kinase C (PKC). Given the central role of PKC isoforms in cellular signaling, along with their differential biological activities, a critical objective is the design of isoform selective ligands. Here, we report the synthesis of a series of DAG-lactones varying in their side chains, with a particular focus on linoleic acid derivatives. We evaluated their selectivity for PKC epsilon versus PKC alpha both under standard lipid conditions (100% phosphatidylserine, PS) as well as in the presence of a nuclear membrane mimetic lipid mixture (NML). We find that selectivity for PKC epsilon versus PKC alpha tended to be enhanced in the presence of the nuclear membrane mimetic lipid mixture and, for our lead compound, report a selectivity of 32-fold.
- Ann, Jihyae,Yoon, Suyoung,Baek, Jisoo,Kim, Da Hye,Lewin, Nancy E.,Hill, Colin S.,Blumberg, Peter M.,Lee, Jeewoo
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p. 332 - 341
(2015/05/04)
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- Synthesis of new 123I-labeled free fatty acids analogues and first evaluation as potential tracers for SPECT imaging to elucidate fatty acid flux in mouse
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The aim of our study was to synthesize new radiotracers for in vivo imaging to examine the metabolic fate of fatty acids according to their unsaturation degree. Three different fatty acids of the 18-carbon series have been synthesized, labeled with 123I, and their biodistribution has been evaluated in mice in vivo. The main result shows a different distribution pattern of the fatty acids according to their degree of unsaturation between the white adipose tissue and the muscles, which is coherent with previous studies using stable isotopes. The Royal Society of Chemistry 2013.
- Ouadi, Ali,Habold, Caroline,Keller, Murielle,Bekaert, Virgile,Brasse, David
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p. 19040 - 19050
(2013/10/22)
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- Carbon-carbon bond fission on oxidation of primary alcohols to carboxylic acids
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α-Carbon-carbon bond cleavage is shown to be a general side reaction accompanying the oxidation of unbranched primary alcohols to the corresponding carboxylic acids using HNO3, CrO3/H2SO 4/H2O/acetone, CrO3/CH3COOH, PDC/DMF, H5IO6/CrO3, KMnO4/H +, KMnO4/HO-, NiCl2/NaClO, TEMPO/PhI(OAc)2. Therefore, the product formed is always contaminated with a carboxylic acid containing one carbon atom less. Systems such as PhI(OAc)2/TEMPO or H5IO6/CrO 3/CH3CN reduce to a minimum the content of this impurity. Temperature, the order of reagent addition, and additives such as oxalic acid or cerium salts produce a profound effect on the formation of the undesirable impurity during the Jones oxidation of primary alcohols.
- Bekish, Andrei V.
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scheme or table
p. 3082 - 3085
(2012/07/28)
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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.
-
supporting information; experimental part
p. 430 - 439
(2011/04/16)
-
- Mild method for the selective esterification of carboxylic acids based on the Garegg-samuelsson reaction
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A mild method for the selective esterification of primary alcohols is described. The use of different phosphines, I2, and imidazole allows the selective esterification of a wide variety of acids with excellent results. The generation of a bulky phosphonium-carboxylate salt as intermediate could justify the selectivity observed in this process. Additionally, amides also can be synthesized with use of this method.
- Morcillo, Sara P.,Alvarez De Cienfuegos, Luis,Mota, Antonio J.,Justicia, Jose,Robles, Rafael
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supporting information; experimental part
p. 2277 - 2281
(2011/05/19)
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- TPAP-catalyzed direct oxidation of primary alcohols to carboxylic acids through stabilized aldehyde hydrates
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We present a simple, mild, and highly effective method for the direct conversion of primary alcohols to carboxylic acids. TPAP serves as the catalyst, and NMO?H2O plays a dual role, acting as the co-oxidant and as a reagent for aldehyde hydrate stabilization. This previously unknown stabilizing effect of geminal diols by N-oxides is the key for the efficiency of the overall transformation.
- Schmidt, Andrea-Katharina C.,Stark, Christian B. W.
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supporting information; experimental part
p. 4164 - 4167
(2011/10/08)
-
- 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 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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p. 1591 - 1596
(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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- A facile formal synthesis of volicitin
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A short and concise synthesis of volicitin is presented. The synthesis is based on repeated chemoselective copper salt cross coupling reactions of alkynes and propargylic halides.
- Hansen, Trond Vidar,Stenstrom, Yngve
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p. 2549 - 2557
(2007/10/03)
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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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- Useful Direct Conversion of Tetrahydropyranyl Ethers of Fatty Alcohols into Fatty Acids
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Tetrahydro-2-pyranyl ethers from fatty primary alcohols can be converted in a one-step procedure into the corresponding carboxylic acids in high yields.This process avoids the synthesis of symmetrical esters, particularly for long-chain compounds.This reaction proved to be useful, for instance, to produce polyunsaturated fatty acids immediately before their biological testing. - Key words: Oxidation; polyunsaturated fatty acids; tetrahydropyranyl ethers
- Gruiec, Regine,Noiret, Nicolas,Patin, Henri
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p. 1083 - 1085
(2007/10/03)
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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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- 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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- An Isotopic Study (2H and 18O) of the Enzymatic Conversion of Linoleic Acid into Colneleic Acid with Carbon Chain Fracture: the Origin of Shorter Chain Aldehydes
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Contrary to earlier reports, the divinyl 9-ether oxygen of colneleic acid is shown by experiment with 18O2 to originate from oxygen, not water.Using -9(S)-hydroperoxyoctadeca-10(E),12(Z)-dienoic acid, made enzymatically from synthetic linoleic acid, it is found that the distribution of deuterium as determined by NMR and mass spectrometry in the fractured carbon chain of colneic acid formed by potato enzyme, is consistent with the intervention of an epoxy carbonium ion intermediate.Though divinyl acids such as colneleic and colnelenic acid give the expected shorter chain aldehydes on treatment with aqueous acid, it is likely that the latter are formed in most plants by trapping of a monovinyl oxonium ion rather than by rehydration of colneleic and colnelenic acid.
- Crombie, Leslie,Morgan, David O.,Smith, Elisabeth H.
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p. 567 - 575
(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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- A GENERAL METHOD FOR THE SYNTHESIS OF DIACETYLENIC ACIDS
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A simple and convenient method for the synthesis of twelve novel alkadiynoic acids, HOOC(CH2)mCC-C-CC(CH2)n-CH3, is reported.
- Singh, Alok,Schnur, Joel M.
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p. 847 - 852
(2007/10/02)
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- STRUCTURES AND SYNTHESIS OF SEED-GERMINATION INHIBITORS FROM HIBISCUS ROSA-SINENSIS
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Key Word Index - Hibiscus rosa-sinensis; Malvaceae; seed germination; inhibition; acetylenic acids; o-nitrophenyl selenide. 8-Nonynoic, 9-decynoic acids and their methyl esters were isolated for the first time as natural products from Hibiscus rosa-sinensis.They were inhibitors of the germination of lettuce seeds and were synthesized via o-nitrophenyl selenides.
- Nakatani, Munehiro,Yamachika, Takashi,Tanoue, Takao,Hase, Tsunao
-
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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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