- Design, Synthesis, and Biological Evaluation of the Sex Pheromone of the Asian Corn Borer, Ostrinia furnacalis (Guenée)
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A convenient total synthesis of (Z)-12-tetradecenyl acetate (1a) and (E)-12-tetradecenyl acetate (1b), which are the sex pheromones of Ostrinia furnacalis (Guenée), has been achieved. The target mixture molecules, of a cis-to-trans-isomer ratio of 27 to 73, were synthesized in 40% overall yield and through [13C + 1C] synthetic strategy in five steps from commercially available and cheap industrial brassylic acid as key starting material. The electroantennogram (EAG) responses of synthetic sex pheromone to ACB male moths were conducted. The results showed that the target mixture molecules were found to have a good activity and displayed significantly stronger EAG responses ranging from 10 to 1000 μg, and the optimized stimulating dosage of the activity of synthetic sex pheromone to ACB males is 10 μg. Compared with the existing routes, this synthetic approach is operationally simple, good-yielding, and cost-effective, which could serve as a basis for developing the techniques of sex pheromone mass trapping or mating disruption and providing an environmentally benign method to control ACB pests.
- Lu, Zhengchang,Liu, Wei,Pan, Hongyu,Zhang, Dawei
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- The first examples of a Meta-benzannulation from the reaction of Fischer carbene complexes with alkynes
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The intramolecular benzannulations of carbene complexes with alkynes are examined where the alkyne is tethered to the α-carbon of the vinyl carbene complex. These reactions are sensitive to the length of the tether and to the nature of the solvent. With a tether length of 16 methylenes, the reaction occurs in the same fashion as the intermolecular reactions to give a p-cyclophane. With intermediate tether lengths (n = 10, 13), the reaction gives an additional p-cyclophane in which the two oxygen substituents are meta on the arene ring. This type of product is unprecedented from the reaction of carbene complexes and alkynes and is quite surprising because the formation of this product requires that the carbon-carbon bond between the α- and β-carbons of the vinyl carbene complex is broken. A mechanism is proposed to account for this process which involves the crossed intramolecular [2 + 2] cycloaddition of the alkene and a ketene in a conjugated dienyl ketene to give a benzvalenone paddalane intermediate. Copyright
- Wang, Huan,Huang, Jie,Wulff, William D.,Rheingold, Arnold L.
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- Heat capacities near room temperature of ten solid alkane-α, ω-diols HO-(CH2)n-OH where n = 6 and 8 ≤ n ≤ 16
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The molar heat capacities at constant pressure Cp,m of a homologous series of alkane-α, ω-diols HO-(CH2)n-OH, where n has values of 6 and (8 to 16), were determined by using differential scanning calorimetry over the temperature range (280 to 310) K, in flowing gas. The measured values of Cp,m showed a very good linear dependence on temperature, except 1,9-nonanediol and 1,13-tridecanediol. The heat capacities at T = 298.15 K were obtained by interpolating the smoothed fitting equations as a function of temperature. The contribution to the heat capacity at T = 298.15 K of the CH2 group was derived from the slope of the Cp,m values of diols as a function of the number of carbon atoms in their molecules, and compared with the values obtained from a comprehensive collection of literature data for homologous alkyl organic compounds in the solid state. 1999 Academic Press.
- Della Gatta, Giuseppe,Jozwiak, Malgorzata,Ferloni, Paolo
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- Selective Reduction of Carboxylic Acids to Alcohols in the Presence of Alcohols by a Dual Bulky Transition-Metal Complex/Lewis Acid Catalyst
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Here, we report a molecular method for the generally applicable reduction of mono-and dicarboxylic acids that selectively furnishes a diverse variety of alcohols, including mono-and diols. One of the inherent drawbacks of the direct hydrogenation of carboxylic acids to alcohols is the in situ formation of the corresponding esters via condensation of the carboxylic acids with the produced alcohols. Especially, the hydrogenation of polycarboxylic acids frequently suffers from the formation of a complex mixture of oligomeric esters. This issue was successfully overcome by the combined use of a dual catalyst that consists of a bulky (PNNP)iridium complex and a Lewis acid. Owing to the steric bulk and robustness of the iridium catalyst, the main role of the Lewis acid is to independently catalyze the esterification, albeit the cooperative activation of (a resting state of) the iridium catalyst by the Lewis acid also seems to be implied.
- Gr?mer, Bendik,Saito, Susumu,Yoshioka, Shota
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p. 1957 - 1964
(2022/02/10)
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- Synthesis of 13C-labelled ω-hydroxy carboxylic acids of the general formula HO213C-(CH2)n-CH2OH or HO2C-(CH2)n-13CH2OH (n = 12, 16, 20, 28)
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13C-labelled ω-hydroxy-carboxylic acids HO213C-(CH2)n-CH2OH or HO2C-(CH2)n-13CH2OH (n = 12, 16, 20, 28) with 13C labels selectively introduced either at the carboxy group or at the primary alcohol function at the end of the hydrocarbon chain have been synthesized. Different synthetic strategies had to be applied depending on the position of the label, the chain length of the respective synthetic target and due to economic considerations. 13C labels in general were introduced by nucleophilic substitution of a suitable leaving group with labelled potassium cyanide and subsequent hydrolysis of the nitriles to produce the corresponding labelled carboxy functions, which may also be reduced to give the labelled primary alcohol group. All new compounds are characterized by GC/MS, IR and NMR methods as well as by elemental analysis.
- Schink, Carina,Spielvogel, Sandra,Imhof, Wolfgang
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p. 385 - 402
(2021/07/10)
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- METABOLICALLY STABLE PRODRUGS
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Provided are prodrugs of various therapeutic agents that provide enhanced bioavilabilty of the therapeutic agent, and methods of treatment conditions in a subject by administration of the one or prodrugs. As provided herein a prodrug includes a therapeutic agent covalently attached to a cap, the cap having a structure according to formula (I) where: R1 is a branched or linear substituted or unsubstituted C2-C6 alkyl, alkenyl, or alkynl; X is -S(0)2-; R2 is a branched or linear substituted or unsubstituted C4-C20 alkyl, alkenyl, or alkynyl; and R3 is -H, C3-C5 cycloalkyl, C3-C5 cycloheteroalkyl, -C(CH3)3, -CF3, -C(CF3)3, or a substituted or unsubstituted phenyl.
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Paragraph 00119
(2020/01/24)
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- Systematic synthesis of novel phosphoglycolipid analogues as potential agonists of GPR55
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Rhodopsin-like G protein-coupled receptor (GPCR) GPR55 is attracting attention as a pharmaceutical target, because of its relationship with various physiological and pathological events. Although GPR55 was initially deorphanized as a cannabinoid receptor,
- Abe, Junpei,Ding, Feiqing,Greimel, Peter,Guy, Adam T.,Hirabayashi, Yoshio,Ito, Yukishige,Kamiguchi, Hiroyuki
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supporting information
p. 8467 - 8473
(2020/11/05)
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- Chemical synthesis of diglucosyl diacylglycerols utilizing glycosyl donors with stereodirecting cyclic silyl protective groups
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Chemical syntheses of the bacterial diglucosyl diacylglycerols 1-heptadecanoyl-2-pentadecanoyl-3-O-[6-O-(β-d-glucopyranosyl)-β-d-glucopyranosyl]-sn-glycerol and 1-(cis-13-octadecenoyl)-2-palmitoyl-3-O-[2-O-(α-d-glucopyranosyl)-α-d-glucopyranosyl]-sn-glycerol are described. The syntheses feature the stereoselective construction of glycosidic linkages in glycosylation reaction by utilizing glycosyl donors with stereodirecting cyclic silyl protective groups. The 1,1,3,3-tetraisopropyldisiloxane-1,3-diyl (TIPDS) group was used for formation of the β-glycosidic linkage, while the di-tert-butylsilylene (DTBS) group was used for α-linkage formation. The silyl protective groups were chemoselectively cleavable without affecting acyl functionalities on the glycerol moiety and proved effective for the synthesis of diacylglycoglycerolipids.
- Takato, Koichi,Kurita, Motoki,Yagami, Nahoko,Tanaka, Hide-Nori,Ando, Hiromune,Imamura, Akihiro,Ishida, Hideharu
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- A Synthetic Route to the MT1-MMP Inhibitor Ancorinoside D
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A methyl ester of ancorinoside D, a 3-acyltetramic acid metabolite of a sponge Penares sollasi, was synthesised in ten steps starting from a protected β- d -glucopyranosyl-(1→4)- d -galactopyranosyltrichloroacetimidate donor. Its attachment to the left half of the 3-acyl spacer by a Schmidt glycosylation, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation to the uronic acid, introduction of the Z -alkene via Wittig reaction, and functionalisation of the spacer terminus with Meldrum's acid gave a β-keto ester that reacted with dimethyl N -methyl- d -aspartate under neutral conditions to afford a fully protected ancorinoside D as the product of an unusual domino N -acylation-Dieckmann condensation. Global deprotection left a methyl ester of ancorinoside D, which resisted all saponification attempts.
- Petermichl, Markus,Steinert, Christine,Schobert, Rainer
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p. 730 - 738
(2019/01/23)
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- Hydrofunctionalization of olefins to value-added chemicals: Via photocatalytic coupling
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A green strategy was developed for the synthesis of various value-added chemicals using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the hydrogen source by coupling them with olefins over heterogeneous photocatalysts. A radical coupling mechanism was proposed for the hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over the Pt/TiO2 catalyst as the model reaction. C-H bond cleavage and C-C bond formation between photogenerated radicals and terminal olefins were accomplished in a single reaction at high efficiency. Our approach is atomically economical with high anti-Markovnikov regioselectivity and promising application potential under mild reaction conditions.
- Fan, Yonghui,Li, Shenggang,Bao, Jingxian,Shi, Lei,Yang, Yanzhang,Yu, Fei,Gao, Peng,Wang, Hui,Zhong, Liangshu,Sun, Yuhan
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supporting information
p. 3450 - 3456
(2018/08/06)
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- From intermolecular interactions to texture in polycrystalline surfaces of 1,ω-alkanediols (ω = 10–13)
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Differences on herringbone molecular arrangement in two forms of long-chain 1,?-alkanediols (CnH2n+2O2 with n = 10, 11, 12, 13) are explained from the analysis of O-H···O hydrogen-bond sequences in infinite chains and the role of a C-H···O intramolecular hydrogen-bond in stabilization of a gauche defect, as well as the inter-grooving effectiveness on molecular packing. GIXD (Glancing Incidence X-ray Diffraction) experiments were conducted on polycrystalline monophasic samples. Diffracted intensities were treated with the multi-axial March-Dollase method to correlate energetic and geometrical features of molecular interactions with the crystalline morphology and textural pattern of samples. The monoclinic (P21/c, Z = 2) crystals of the even-numbered members (n = 10, 12; DEDOL and DODOL, respectively) are diametrical prisms with combined form {104}/{-104}/{001} and present a two-fold platelet-like preferred orientation, whereas orthorhombic (P212121, Z = 4) odd-numbered members (n = 11, 13; UNDOL and TRDOL, respectively) present a dominant needle-like orientation on direction [101] (fiber texture). We show that crystalline structures of medium complexity and their microstructures can be determined from rapid GIXD experiments from standard radiation, combined with molecular replacement procedure using crystal structures of compounds with higher chain lengths as reference data.
- Luis-Raya, Gilgamesh,Ramírez-Cardona, Màrius,Luna-Bárcenas, Gabriel,Hernández-Landaverde, Martín A.,Jiménez-Nieto, Adair,García-Rivas, Jose Luis,Espa A-Sánchez, Beatriz Liliana,Sanchez, Isaac C.
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- Synthesis of ceramides NS and NP with perdeuterated and specifically ω deuterated N-acyl residues
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The synthesis of 12 deuterated ceramides with either a deuteration at the last carbon atom of the amide bound fatty acid or a perdeuterated fatty acid chain is described. The ceramides were prepared starting from sphingosine or phytosphingosine and ω deuterated or perdeuterated fatty acids with PyBOP as activating agent in high yields. For the synthesis of the specifically deuterated fatty acids, dicarboxylic acids were transformed into ω deuterated alkyl bromide, which was chain elongated with blocked ω bromo alcohols by copper catalyzed Grignard coupling. Oxidation of regenerated alcohol function yields the ω deuterated fatty acids.
- Sonnenberger, Stefan,Lange, Stefan,Langner, Andreas,Neubert, Reinhard H.H.,Dobner, Bodo
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p. 531 - 542
(2016/11/06)
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- Liposomes containing tetraether lipid derivatives
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The present invention relates to liposomes comprising a tetraether lipid of formula (1) or a salt thereof and at least one sterol, wherein the molar ratio of tetraether lipid to sterol is from 1 : 1 to 1 : 10.
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Page/Page column 16
(2014/04/04)
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- The anti-malarial activity of bivalent imidazolium salts
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A series of compounds containing bivalent imidazolium rings and one triazolium analog were synthesized and evaluated for their ability to inhibit the replication of Plasmodium falciparum cultures. The activity and selectivity of the compounds for P. falciparum cultures were found to depend on the presence of electron-deficient rings that were spaced an appropriate distance apart. The activity of the compounds was not critically dependent on the nature of the linker between the electron-deficient rings, an observation that suggests that the rings were responsible for the primary interaction with the molecular target of the compounds in the parasite. The bivalent imidazolium and triazolium compounds disrupted the process whereby merozoites gain entry into erythrocytes, however, they did not appear to prevent merozoites from forming. The compounds were also found to be active in a murine Plasmodium berghei infection, a result consistent with the compounds specifically interacting with a parasite component that is required for replication and is conserved between two Plasmodium species.
- Vlahakis, Jason Z.,Mitu, Simona,Roman, Gheorghe,Rodriguez, E. Patricia,Crandall, Ian E.,Szarek, Walter A.
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experimental part
p. 6525 - 6542
(2011/12/02)
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- General synthesis and aggregation behaviour of a series of single-chain 1,ω-Bis(phosphocholines)
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The synthesis and physicochemical characterisation of a series of polymethylene-1,ω-bis(phosphocholines) with even-numbered chain lengths between 22 and 32 carbon atoms is described. Two new synthetic strategies for the preparation of long-chain 1,ω-diols as hydrocarbon building blocks are presented. The temperature-dependent self-assembly of the single-chain bolaamphiphiles was investigated by cryo transmission electron microscopy (cryo-TEM), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR).
- Drescher, Simon,Meister, Annette,Blume, Alfred,Karlsson, Goeran,Almgren, Mats,Dobner, Bodo
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p. 5300 - 5307
(2008/02/11)
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- Synthesis and mass spectrometric analysis of cyclostellettamines H, I, K and L
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Very recently the new cyclostellettamines H, I, K and L were identified from a Brazilian sponge of the genus Pachychalina. They were isolated together with the known cyclostellettamines A-G in a mixture of only 1.5 mg. To obtain further material for biological investigations, the synthesis of the four new cyclostellettamines has been carried out. Since mass spectrometry plays an essential role in identifying these compounds a systematic analysis of the cyclostellettamines is discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Grube, Achim,Timm, Christoph,Koeck, Matthias
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p. 1285 - 1295
(2007/10/03)
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- Quinol fatty alcohols as promoters of axonal growth
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The synthesis of three series of quinol fatty alcohols (QFAs) and their biological activities on the promotion of axonal growth are described. Interestingly, the 15-(2,5-dimethoxyphenyl)pentadecan-1-ol, the QFA bearing 15 carbon atoms on the side chain (n = 15), shows the most potent promotion of axonal growth in the presence of both permissive and non-permissive naturally occurring substrates such as Sema3A and myelin proteins.
- Hanbali, Mazen,Vela-Ruiz, Marta,Bagnard, Dominique,Luu, Bang
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p. 2637 - 2640
(2007/10/03)
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- Effects of indole fatty alcohols on the differentiation of neural stem cell derived neurospheres
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In a search for inducers of neuronal differentiation to treat neurodegenerative diseases such as Alzheimer's disease, a series of indole fatty alcohols (IFAs) were prepared, 13c (n = 18) was able to promote the differentiation of neural stem cell derived neurospheres into neurons at a concentration of 10 nM. Analysis of the expression of the Notch pathway genes in neurospheres treated during the differentiation phase with 13c (n = 18) revealed a significant decrease in the transcription of the Notch 4 receptor.
- Coowar, Djalil,Bouissac, Julien,Hanbali, Mazen,Paschaki, Marie,Mohier, Eliane,Luu, Bang
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p. 6270 - 6282
(2007/10/03)
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- Zirconium borohydride - A versatile reducing agent for the reduction of electrophilic and nucleophilic substrates
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Zirconium borohydride, a potential reducing agent, reduces acids, esters, imines to the corresponding alcohols and secondary amines in good yield at room temperature within two hours. This facile reducing property was taken advantage off in the synthesis of pheromones and some novel chiral precursors for asymmetric synthesis.
- Narasimhan,Balakumar
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p. 4387 - 4395
(2007/10/03)
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- Effect of cyclohexenonic long chain fatty alcohols on neurite outgrowth. Study on structure-activity relationship
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Four series of long chain fatty alcohols bearing a cyclohexenone moiety in addition to a ω-alkanol side chain were synthesized using 'Umpolung' reactivity strategy. Their effect on neurite outgrowth was evaluated by means of fetal rat neurons in culture. The length of the ω-hydroxy side chain is a crucial factor for biological activity.
- Girlanda-Junges, Celine,Keyling-Bilger, Florence,Schmitt, Gaby,Luu, Bang
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p. 7735 - 7748
(2007/10/03)
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- A simple alkene-catalyzed reduction of aromatic esters to alcohols by zinc borohydride
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Reactivity of Zn(BH4)2 was modified by adding cyclohexene to achieve the reduction of aromatic esters to alcohols which reaction was not possible previously because of the mild nature of the reagent. Functional groups like Cl and nitro were tolerated.
- Narasimhan,Madhavan,Ganeshwar Prasad
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p. 385 - 390
(2007/10/03)
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- Hydrogenation of carboxylic acids using bimetallic catalysts consisting of Group 8 to 10, and Group 6 or 7 metals
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Hydrogenation of carboxylic acids to alcohols was effectively catalyzed by bimetallic systems consisting of Group 8 to 10 late transition-metals, and Group 6 or 7 early transition-metal carbonyls. These catalysts easily converted α,ω-dicarboxylic acid monoesters into ω-hydroxyalkanoic esters in good yields.
- He, De-Hua,Wakasa, Noriko,Fuchikami, Takamasa
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p. 1059 - 1062
(2007/10/02)
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- Pheromone Synthesis, CLXIII. Synthesis of (9Z,25S,26R,43Z)-25,26-Epoxy-9,43-henpentacontadiene and Its Antipode, Components of the Nymph Recognition Pheromone Produced by Nymphs of the Cockroach Nauphoeta cinerea
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(9Z,25S,26R,43Z)-25,26-Epoxy-9,43-henpentacontadiene (1) and its antipode, the nymph recognition pheromone of Nauphoeta cinerea, were synthesized by extending the carbon chain of (2S,3R)-4-acetoxy-2,3-epoxy-1-butanol (25).The Grignard coupling was the key
- Mori, Kenji,Argade, Narshinha P.
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p. 695 - 700
(2007/10/02)
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- Improved method for the selective conversion of aliphatic esters to alcohols by zinc borohydride in tetrahydrofuran
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Selective conversion of aliphatic esters to the corresponding alcohols has been achieved in excellent yields by zinc borohydride in tetrahydrofuran under mild conditions (67 deg C, 6 hr).Unsaturated esters produce the corresponding diols.
- Narasimhan, S,Palmer, Prem
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p. 701 - 702
(2007/10/02)
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- Lactones. 2. Enthalpies of hydrolysis, reduction, and formation of the C4-C13 monocyclic lactones. Strain energies and conformations
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The enthalpies of hydrolysis of the monocyclic lactones from γ-butyrolactone to tridecanolactone were determined calorimetrically, and the acyclic ethyl having the number of atoms were studied in the fashion. The enthalpies of reduction of the lactones to the corresponding α,ω-alkanediols with lithium triethylborohydride also were determined. The enthalpies of formation of the lactones and the ethyl esters were derived from these data. They were converted to values for the gas phase by measuring the enthalpies of vaporization of ethyl esters and of lactones. In the of γ-butyrolactone and δ-valerolactone, the enthalpies of formation were in good accord with the previously reported values determined via combustion calorimetry. The strain energies of the lactones were obtained via isodesmic reactions. Valerolactone had a strain energy of 11 kcal/mol, and the largest strain energy was found with octanolactone (13 kcal/mol). The conformations of γ-butyrolactone and δ-valerolactone were studied via MP2/6-31G* geometry optimizations, and the conformations of the other lactones were studied with use of the molecular mechanics program MM3. The energies of the lactones estimated via molecular mechanics were compared with the experimental results.
- Wiberg, Kenneth B.,Waldron, Roy F.
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p. 7697 - 7705
(2007/10/02)
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- Synthesis of Sphingosine Relatives, IX. Synthesis of (2S,3R,4E)-1-O-(β-D-Glucopyranosyl)-N--4-sphingenine. The Structure Proposed for the Esterified Cerebroside in the Epidermis of Guinea Pigs
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(2S,3R,4E)-1-O-(β-D-Glucopyranosyl)-N--4-sphingenine (1) was synthesized from D-glucose (A), (2S,3R,4E)-4-sphingenine (sphingosine, B), 24-hydroxytetracosanoic acid (C) and linoleic acid (D).The 1H-NMR spectrum of the synthetic 1 was different from that of the esterified cerebroside which was isolated as a tissue-characteristic compound in the epidermis of foodpad and dorsal skin of guinea pigs.
- Mori, Kenji,Nishio, Hiroyuki
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p. 253 - 257
(2007/10/02)
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- Stereoselective Synthesis of Octadeacpolyenoic Esters as an Insecticide
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Octadecapolyenoic acid derivatives such as (+/-)-t-butyl coriolate, α-eleostearic acid, t-butyl punicate, and t-butyl (9Z,11E)-13-hydroxy-9,11-octadien-15-ynoate were synthesized starting from oleic acid with high stereoselectivity and their insecticidal
- Tsuboi, Sadao,Wu, Xue Han,Maeda, Seiji,Ono, Shinichiro,Kuroda, Akihisha,et al.
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p. 1103 - 1108
(2007/10/02)
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- Synthesis of 14-hydroxytetra- and 15-hydroxypentadecanoic acids
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14-Hydroxytetradecanoic and 15-hydroxypentadecanoic acids were synthesized from 1,10-decanedicarboxylic and 1,11-undecanedicarboxylic acids.The diesters of the latter were reduced to the diols, from which the chlorohydrins were obtained by reaction with hydrogen chloride.The use of these chlorohydrins in the sodiomalonic synthesis leads to the hydroxy carboxylic acids.
- Zakharkin, L. I.,Guseva V. V.,Pryanishnikov A. P.
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p. 658 - 661
(2007/10/02)
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