- Total Synthesis of Atisane-Type Diterpenoids: Application of Diels-Alder Cycloadditions of Podocarpane-Type Unmasked ortho-Benzoquinones
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Few examples of [4 + 2] cycloaddition with unmasked ortho-benzoquinones (UMOBs) as carbodiene have been reported in complex molecule synthesis. Herein we report that this cycloaddition with podocarpane-type UMOB was developed and applied to construct fully functionalized bicyclo[2.2.2]octanes. Based on this methodology, divergent total syntheses of atisane-type diterpenoids, including (±)-crotobarin, crotogoudin, atisane-3β,16α-diol, and 16S,17-dihydroxy-atisan-3-one, were accomplished in 14, 14, 12, and 16 steps, respectively. Key elements in these total syntheses include: (1) FeCl3-catalyzed cationic cascade cyclization to construct podocarpane-type skeleton; (2) Mn(III)/Co(II)-catalyzed radical hydroxylation of alkene with high regio-, diastereo-, and chemoselectivities; (3) and a ketal-deprotection/lactone-opening/deprotonation/lactonization cascade. Additionally, the synthetic utility of the fully functionalized bicyclo[2.2.2]octane framework was further elucidated by applying ring distortion strategy to afford different skeleton-rearranged natural product-like compounds.
- Song, Liqiang,Zhu, Guili,Liu, Yongjiang,Liu, Bo,Qin, Song
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- Preparation of 2,6-difluoromanoalogues derivatives
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Design of the inhibitors for the phospholipase A2 modified with fluorine(s) and total synthesis of 2,6-difluoromanoalogues derivatives, are described.
- Komatsu, Yuzo,Kitazume, Tomoya
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- Geraniol grafted chitosan oligosaccharide as a potential antibacterial agent
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The novel derivatives of geraniol grafted chitosan oligosaccharide were synthesized via substitution and deprotection reaction, respectively. The products were identified by Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), X-ray diffraction analysis (XRD), Thermogravimetric analysis (TGA) and UV–vis absorption spectroscopy. It is revealed that the derivatives exhibited a good solubility, thermal stability and antibacterial properties.
- Yue, Lin,Li, Jingru,Chen, Wanwen,Liu, Xiaoli,Jiang, Qixing,Xia, Wenshui
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- Total Synthesis of C30 Botryococcene and epi-Botryococcene by a Diastereoselective Ring Opening of Alkenylcyclopropanes
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Trialkylaluminum compounds perform a diastereoselective 1,6-ring fragmentation of alkenylcyclopropane. This new tool allows the preparation of hydrocarbon compounds containing two distant stereocenters with a good diastereocontrol. Inspired by the biosynthesis of botryococcene this methodology was applied successfully to the diastereo- and enantioselective preparation of this triterpene and its epimer.
- Cormier, Morgan,de la Torre, Aurélien,Marek, Ilan
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- (-)-Axinyssene: A novel cytotoxic diterpene from a Japanese marine sponge Axinyssa sp
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(Matrix presented) A novel diterpene, (-)-axinyssene, was isolated from the Japanese marine sponge Axinyssa sp. The structure of (-)-axinyssene was determined on the basis of spectroscopic and synthetic evidence to be 1-methyl-4-[(4E)-5′9′-dimethyl-1′-methylene-4′, 8′-decadienyl]-(4S)-cyclohexene. (-)- and (+)-axinyssene showed mild cytotoxicity against acute promyelocytic leukemia, HL-60 cells.
- Kodama, Kota,Higuchi, Ryuichi,Miyamoto, Tomofumi,Van Soest, Rob W. M.
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- Triazole-based inhibitors of geranylgeranyltransferase II
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A small set of triazole bisphosphonates has been prepared and tested for the ability to inhibit geranylgeranyltransferase II (GGTase II). The compounds were prepared through use of click chemistry to assemble a central triazole that links a polar head group to a hydrophobic tail. The resulting compounds were tested for their ability to inhibit GGTase II in an in vitro enzyme assay and also were tested for cytotoxic activity in an MTT assay with the human myeloma RPMI-8226 cell line. The most potent enzyme inhibitor was the triazole with a geranylgeranyl tail, which suggests that inhibitors that can access the enzyme region that holds the isoprenoid tail will display greater activity.
- Zhou, Xiang,Hartman, Sara V.,Born, Ella J.,Smits, Jacqueline P.,Holstein, Sarah A.,Wiemer, David F.
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- Rapid library synthesis of amphiphiles based on a dioxinone scaffold and identification of nonlamellar liquid crystals
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Linear and branched amphiphiles with different lengths of lipids and different numbers of hydroxyl groups were rapidly synthesized based on a dioxinone scaffold. The liquid crystalline (LC) properties of the synthesized amphiphiles in excess water were investigated by polarizing optical microscopy and small-angle X-ray scattering (SAXS) analysis. Novel β-keto ester based amphiphiles that formed non-lamellar, inverted LC phases were identified.
- Fuse, Shinichiro,Nakamura, Kentarou,Mifune, Yuto,Marubayashi, Hironori,Hijikuro, Ichiro,Nojima, Shuichi,Tanaka, Hiroshi,Takahashi, Takashi
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- Design, synthesis, and biological evaluation of novel FXR agonists based on auraptene
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Farnesoid X receptor (FXR) has been considered as an attractive target for metabolic disorder and liver injury, while many current FXR agonists suffer from undesirable side effects, such as pruritus. Therefore, it is urgent to develop new structure types different from current FXR agonists. In this study, a series of structural optimizations were introduced to displace the unstable coumarin and geraniol scaffolds of auraptene (AUR), a novel and safe FXR agonist. All of these efforts led to the identification of compound 14, a potent FXR agonist with nearly fourfold higher activity than AUR. Molecular modeling study suggested that compound 14 fitted well with binding pocket, and formed the key ionic bond with His291 and Arg328. In acetaminophen-induced acute liver injury model, compound 14 exerts better therapeutic effect than that of AUR, which highlighting its pharmacological potential in the treatment of drug-induced liver injury.
- Qiu, Qianqian,Wang, Yanjuan,Gu, Guolong,Yu, Fan,Zhang, Shichao,Zhao, Yining,Ling, Bai
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- Novel tdp1 inhibitors based on adamantane connected with monoterpene moieties via heterocyclic fragments
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Tyrosyl-DNA phosphodiesterase 1 (Tdp1) is a promising target for anticancer therapy due to its ability to counter the effects topoisomerase 1 (Top1) poison, such as topotecan, thus, decreasing their efficacy. Compounds containing adamantane and monoterpenoid residues connected via 1,2,4-triazole or 1,3,4-thiadiazole linkers were synthesized and tested against Tdp1. All the derivatives exhibited inhibition at low micromolar or nanomolar concentrations with the most potent inhibitors having IC50 values in the 0.35–0.57 μM range. The cytotoxicity was determined in the HeLa, HCT-116 and SW837 cancer cell lines; moderate CC50 (μM) values were seen from the mid-teens to no effect at 100 μM. Furthermore, citral derivative 20c, α-pinene-derived compounds 20f, 20g and 25c, and the citronellic acid derivative 25b were found to have a sensitizing effect in conjunction with topotecan in the HeLa cervical cancer and colon adenocarcinoma HCT-116 cell lines. The ligands are predicted to bind in the catalytic pocket of Tdp1 and have favorable physicochemical properties for further development as a potential adjunct therapy with Top1 poisons.
- Chepanova, Arina A.,Dyrkheeva, Nadezhda S.,Ilina, Ekaterina S.,Korchagina, Dina V.,Lavrik, Olga I.,Mozhaitsev, Evgenii S.,Munkuev, Aldar A.,Reynisson, Jóhannes,Salakhutdinov, Nariman F.,Suslov, Evgeniy V.,Volcho, Konstantin P.,Zakharenko, Alexandra L.,Zakharova, Olga D.
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- New hybrid compounds combining fragments of usnic acid and monoterpenoids for effective tyrosyl-dna phosphodiesterase 1 inhibition
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Usnic acid (UA) is a secondary metabolite of lichens that exhibits a wide range of biological activities. Previously, we found that UA derivatives are effective inhibitors of tyrosyl-DNA phosphodiesterase 1 (TDP1). It can remove covalent complex DNA-topoisomerase 1 (TOP1) stabi-lized by the TOP1 inhibitor topotecan, neutralizing the effect of the drugs. TDP1 removes damage at the 3′ end of DNA caused by other anticancer agents. Thus, TDP1 is a promising therapeutic target for the development of drug combinations with topotecan, as well as other drugs for cancer treatment. Ten new UA enamino derivatives with variation in the terpene fragment and substituent of the UA backbone were synthesized and tested as TDP1 inhibitors. Four compounds, 11a-d, had IC50 values in the 0.23–0.40 μM range. Molecular modelling showed that 11a-d, with relatively short aliphatic chains, fit to the important binding domains. The intrinsic cytotoxicity of 11a-d was tested on two human cell lines. The compounds had low cytotoxicity with CC50 ≥ 60 μM for both cell lines. 11a and 11c had high inhibition efficacy and low cytotoxicity, and they enhanced topotecan’s cyto-toxicity in cancerous HeLa cells but reduced it in the non-cancerous HEK293A cells. This “protec-tive” effect from topotecan on non-cancerous cells requires further investigation.
- Dyrkheeva, Nadezhda S.,Filimonov, Aleksandr S.,Luzina, Olga A.,Zakharenko, Alexandra L.,Ilina, Ekaterina S.,Malakhova, Anastasia A.,Medvedev, Sergey P.,Reynisson, Jóhannes,Volcho, Konstantin P.,Zakian, Suren M.,Salakhutdinov, Nariman F.,Lavrik, Olga I.
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- Regiospecific Synthesis of Calcium-Independent Daptomycin Antibiotics using a Chemoenzymatic Method
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Daptomycin (DAP) is a calcium (Ca2+)-dependent FDA-approved antibiotic drug for the treatment of Gram-positive infections. It possesses a complex pharmacophore hampering derivatization and/or synthesis of analogues. To mimic the Ca2+-binding effect, we used a chemoenzymatic approach to modify the tryptophan (Trp) residue of DAP and synthesize kinetically characterized and structurally elucidated regiospecific Trp-modified DAP analogues. We demonstrated that the modified DAPs are several times more active than the parent molecule against antibiotic-susceptible and antibiotic-resistant Gram-positive bacteria. Strikingly, and in contrast to the parent molecule, the DAP derivatives do not rely on calcium or any additional elements for activity.
- Mupparapu, Nagaraju,Lin, Yu-Hsin Cindy,Kim, Tae Ho,Elshahawi, Sherif I.
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supporting information
p. 4176 - 4182
(2021/02/01)
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- A mild method for the replacement of a hydroxyl group by halogen: 3. the dichotomous behavior of α-haloenamines towards allylic and propargylic alcohols
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A study of the deoxyhalogenation of allylic and propargylic alcohols with tetramethyl-α-halo-enamines is reported. Primary allylic and primary and secondary propargylic alcohols gave the corresponding halides in high yields. Secondary allylic and propargylic alcohols yielded the corresponding secondary halides but the reaction also produced some rearranged primary halides (I > Br > Cl). The reactions with tertiary allylic and tertiary propargylic alcohols gave several products and was therefore of little synthetic value. However, the addition of triethylamine to the reaction mixture or the use of lithium alkoxide instead of alcohol brought about a major change of the course of the reaction which led to amides carrying an allyl or an allenyl group at C2. This was shown to result from a Claisen-Eschenmoser rearrangement of an intermediate α-allyloxy- or propargyloxy-enamine.
- Munyemana, Fran?ois,Patiny, Luc,Ghosez, Léon
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- Chitooligosaccharide-N-geraniol derivatives, methods for preparing and application thereof
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The present invention provides a chitooligosaccharide-N-geraniol derivative and a preparation method and application thereof. The degree of substitution of a chitooligosaccharide-N-geraniol derivative is from 0.26 to 0.283. The method includes dissolving oligosaccharide in dimethyl sulfoxide, dissolving geranyl bromide in dimethylformamide, and then mixing, performing a water bath reaction and adding acetone in after the water bath reaction, performing a centrifugation and collecting precipitates, performing Soxhlet extraction and vacuum drying to obtain the chitooligosaccharide-N-geraniol derivative. The present invention has the advantages of easy preparation method, low cost, simple purification method and stable properties. The chitooligosaccharide derivative has good water solubility, antibacterial activity against Staphylococcus aureus, Escherichia coli and other bacteria, and has good application prospect in the fields of medicine, food, cosmetics, agriculture, etc.
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(2021/08/11)
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- Asymmetric total synthesis of (–)-rossinone A
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The asymmetric total synthesis of (–)-rossinone A, a meroterpene exhibiting a range of pharmacologically important biological activities, has been accomplished for the first time from geraniol by a concise eight-step sequence that involves the Horner–Wadsworth–Emmons reaction of an aldehyde derived from a geranylated hydroquinone intermediate with a chiral phosphonate prepared via the highly diastereoselective Davis oxidation of a known oxazolidinone derivative.
- Saito, Katsuya,Kurasawa, Kazuki,Takino, Chiaki,Kuwahara, Shigefumi,Enomoto, Masaru
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supporting information
(2021/10/14)
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- Total Synthesis of (+)-Cyclobutastellettolide B
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A convenient enantioselective total synthesis of (+)-cyclobutastellettolide B via a strategy that involves a diastereoselective Johnson-Claisen rearrangement, a regioselective cyclopropoxytrimethylsilane ring-opening reaction, and a Norrish-Yang cyclization is described. The results of computational and experimental studies indicate that the regio- and stereoselectivity of the Norrish-Yang reaction are controlled by the C-H bond dissociation energy and restricted rotation of the C13-C14 bond.
- Zhang, Zhongchao,Chen, Sijia,Tang, Fu,Guo, Kai,Liang, Xin-Ting,Huang, Jun,Yang, Zhen
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supporting information
p. 18287 - 18293
(2021/11/10)
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- METHODS OF SYNTHESIZING FARNESYL DIBENZODIAZEPINONES
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The present invention is directed to synthetic means for producing farnesyl dibenzodiazepinone compounds, including AMO-01.
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Paragraph 0086-0087
(2021/12/08)
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- CHINONE-, HYDROCHINOME- AND NAPHTHOCHINONE-ANALOGUES OF VATIQUIONE FOR TREATMENT OF MITOCHONDRIAL DISORDER DISEASES
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The disclosure provides therapeutic compositions (i.e., therapeutic agents) and methods of preventing or treating Friedreich's ataxia in a mammalian subject, reducing risk factors, signs and/or symptoms associated with Friedreich's ataxia (e.g. Complex I deficiency), and/or reducing the likelihood or severity of Friedreich's ataxia. The disclosure further provides novel intermediates for the production of said therapeutic compositions and related reduced versions of said therapeutic compositions, which reduce forms may also be used as therapeutic agents (or prodrugs of the therapeutic agent(s)).
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Page/Page column 212-213
(2021/04/10)
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- Promising new inhibitors of tyrosyl-DNA phosphodiesterase I (Tdp 1) combining 4- arylcoumarin and monoterpenoid moieties as components of complex antitumor therapy
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Tyrosyl-DNA phosphodiesterase 1 (Tdp1) is an important DNA repair enzyme in humans, and a current and promising inhibition target for the development of new chemosensitizing agents due to its ability to remove DNA damage caused by topoisomerase 1 (Top1) poisons such as topotecan and irinotecan. Herein, we report our work on the synthesis and characterization of new Tdp1 inhibitors that combine the arylcoumarin (neoflavonoid) and monoterpenoid moieties. Our results showed that they are potent Tdp1 inhibitors with IC50 values in the submicromolar range. In vivo experiments with mice revealed that compound 3ba (IC50 0.62 μM) induced a significant increase in the antitumor effect of topotecan on the Krebs-2 ascites tumor model. Our results further strengthen the argument that Tdp1 is a druggable target with the potential to be developed into a clinically-potent adjunct therapy in conjunction with Top1 poisons.
- Ayine-tora, Daniel M.,Chand, Raina,Chepanova, Arina A.,Ilina, Ekaterina S.,Kaledin, Vasily I.,Khomenko, Tatyana M.,Korchagina, Dina V.,Lavrik, Olga I.,Leung, Ivanhoe K. H.,Nikolin, Valeriy P.,Patel, Jinal,Popova, Nelly A.,Reynisson, Jóhannes,Salakhutdinov, Nariman F.,Volcho, Konstantin P.,Zakharenko, Alexandra L.,Zakharova, Olga D.
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- Synthesis of new quaternary ammonium salts with a terpene function and evaluation of their fungicidal and herbicidal activities
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A series of new quaternary ammonium salts (QASs) containing a terpenoid moiety derived from perillyl alcohol, citronellol, and geraniol was synthesized. Structures of all novel compounds were confirmed by spectral methods and elemental analyses. Fungicidal activity of the obtained compounds against six plant pathogens, against four fungi destroying wood and technical materials as well as herbicidal activity against ten species of temperate climate weeds has been examined. Several salts showed a higher antifungal and herbicidal activity than activity of the reference compounds.
- ?elechowski, Krzysztof,Gucma, Miros?aw,Krawczyk, Maria,Marek Go??biewski, W.,Michalczyk, Alicja Katarzyna
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p. 325 - 335
(2020/04/01)
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- Methyl-Shifted Farnesyldiphosphate Derivatives Are Substrates for Sesquiterpene Cyclases
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New sesquiterpene backbones are accessible after biotransformation of presilphiperfolan-8β-ol synthase (BcBOT2), a fungal sesquiterpene synthase, with non-natural farnesyldiphosphates in which methyl groups are shifted by one position toward the diphosphate terminus. One of the macrocycles formed, a new germacrene A derivative, undergoes a Cope rearrangement to iso-β-elemene. Three of the new terpenoids show olfactoric properties that range from an intense peppery note to a citrus, ozone-like, and fruity scent.
- Harms, Vanessa,Schr?der, Benjamin,Oberhauser, Clara,Tran, Cong Duc,Winkler, Sven,Dr?ger, Gerald,Kirschning, Andreas
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supporting information
p. 4360 - 4365
(2020/06/08)
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- Strong antimicrobial activity of collinin and isocollinin against periodontal and superinfectant pathogens in vitro
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Periodontitis pathogenesis involves activation of host immune responses triggered by microbial dysbiosis. Therefore, controlling periodontal pathogens in-vivo is a main goal of periodontal therapy. New antimicrobials might help to control periodontal infection and improve treatment outcomes at “the dark times” of increasing antibiotic resistance. Here, we determined the biological activity of collinin and isocollinin against 8 bacterial strains. Antimicrobial activity of collinin and isocollinin, chlorhexidine digluconate (CHX) and sodium hypochlorite (NaClO) was evaluated against clinically relevant periodontal bacteria, like Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis, Fusobacterium nucleatum, Prevotella intermedia, Dialister pneumosintes strains and superinfectants like Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa strains. A broth microdilution test was carried out to determine the minimum inhibitory concentration of collinin and isocollinin against those strains, and bacterial viability was determined by resazurin assay at diverse concentration and exposure times. P. gingivalis was the most susceptible strain to collinin and isocollinin (MIC 2.1 μg/mL and 4.2 μg/mL respectively). Other periodontal pathogens showed MICs 17 μg/mL for collinin and MICs between 20 and 42 μg/mL for isocollinin, whereas CHX and NaClO showed MICs of 62 and 326 μg/mL, respectively. Collinin and isocollinin also exhibited antimicrobial activity against superinfectant bacteria (MIC 21 and 42 μg/mL, respectively). Overall, collinin and isocollinin showed a remarkable antibacterial activity against relevant periodontal and superinfective bacteria, especially against P. gingivalis (MIC 2.1 μg/mL and 4.2 μg/mL respectively) and the highly virulent P. aeruginosa (MIC 5.2 and 20.8 μg/mL, respectively).
- Bola?os, Gustavo,Contreras, Adolfo,Pardo-Casta?o, Camilo,Vásquez, Daniel
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- The terpenic diamine GIB24 inhibits the growth of Trypanosoma cruzi epimastigotes and intracellular amastigotes, with proteomic analysis of drug-resistant epimastigotes
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The effect of N-geranyl-ethane-1,2-diamine dihydochloride (GIB24), a synthetic diamine, was assayed against different developmental forms of the parasitic protozoan Trypanosoma cruzi (strain Dm28c). The compound was effective against culture epimastigote forms (IC50/24h = 5.64 μM; SI = 16.4) and intracellular amastigotes (IC50/24h = 12.89 μM; SI = 7.18), as detected by the MTT methodology and by cell counting, respectively. Incubation of epimastigotes for 6h with 6 μM GIB24 (IC50/24h value) resulted in significant dissipation of the mitochondrial membrane potential, prior to permeabilization of the plasma membrane. Rounded epimastigotes with cell size reduction were observed by scanning electron microscopy. These morpho-physiological changes induced by GIB24 suggest an incidental death process. Treatment of infected Vero cells did not prevent the intracellular amastigotes from completing the intracellular cycle. However, there was a decrease in the number of released parasites, increasing the ratio amastigotes/trypomastigotes. Proteomic analysis of 15 μM GIB24 resistant epimastigotes indicated that the compound acts mainly on mitochondrial components involved in the Krebs cycle and in maintaining the oxidative homeostasis of the parasites. Our data suggest that GIB24 is active against the main morphological forms of T. cruzi.
- Azeredo, Camila Maria,Barbosa, Gisele,Saraiva, Mauricio Frota,Soares, Maurilio José,de Almeida, Mauro Vieira,de Oliveira, Maristela Ribeiro,de Souza, Marcus Vinicius Nora
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- New chemical agents based on adamantane-monoterpene conjugates against orthopoxvirus infections
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Currently, the spectrum of agents against orthopoxviruses, in particular smallpox, is very narrow. Despite the fact that smallpox is well controlled, there is, for many reasons, a real threat of epidemics associated with this or a similar virus. In order to search for new low molecular weight orthopoxvirus inhibitors, a series of amides combining adamantane and monoterpene moieties were synthesized using 1- and 2-adamantanecarboxylic acids as well as myrtenic, citronellic and camphorsulfonic acids as acid components. The produced compounds exhibited high activity against the vaccinia virus (an enveloped virus belonging to the poxvirus family), which was combined with low cytotoxicity. Some compounds had a selectivity index higher than that of the reference drug cidofovir; the highest SI = 1123 was exhibited by 1-adamantanecarboxylic acid amide containing the (-)-10-amino-2-pinene moiety. The produced compounds demonstrated inhibitory activity against other orthopoxviruses: cowpox virus (SI = 30-406) and ectromelia virus (mousepox virus, SI = 39-707). This journal is
- Agafonov, Alexander P.,Bormotov, Nikolay I.,Korchagina, Dina V.,Maksyutov, Rinat A.,Mozhaytsev, Evgenii S.,Salakhutdinov, Nariman F.,Serova, Olga A.,Shishkina, Larisa N.,Suslov, Evgenii V.,Volcho, Konstantin P.,Yarovaya, Olga I.
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p. 1185 - 1195
(2020/11/03)
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- 4-Methyltetrahydropyran (4-MeTHP): Application as an Organic Reaction Solvent
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4-Methyltetrahydropyran (4-MeTHP) is a hydrophobic cyclic ether with potential for industrial applications. We herein report, for the first time, a comprehensive study on the performance of 4-MeTHP as an organic reaction solvent. Its broad application to organic reactions includes radical, Grignard, Wittig, organometallic, halogen-metal exchange, reduction, oxidation, epoxidation, amidation, esterification, metathesis, and other miscellaneous organic reactions. This breadth suggests 4-MeTHP can serve as a substitute for conventional ethers and harmful halogenated solvents. However, 4-MeTHP was found incompatible with strong Lewis acids, and the C?O bond was readily cleaved by treatment with BBr3. Moreover, the radical-based degradation pathways of 4-MeTHP, THP and 2-MeTHF were elucidated on the basis of GC-MS analyses. The data reported herein is anticipated to be useful for a broad range of synthetic chemists, especially industrial process chemists, when selecting the reaction solvent with green chemistry perspectives.
- Kobayashi, Shoji,Tamura, Tomoki,Yoshimoto, Saki,Kawakami, Takashi,Masuyama, Araki
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p. 3921 - 3937
(2019/11/11)
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- Solubility of Collinin and Isocollinin in Pressurized Carbon Dioxide: Synthesis, Solubility Parameters, and Equilibrium Measurements
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Collinin is a derivative of coumarin that has shown remarkable potential against cancer, tuberculosis, periodontitis, and other prevalent diseases, and is usually extracted from plants of the Rutaceae family at a very low yield. In this work, collinin and a position-isomer herein called isocollinin were synthesized at different scales (from 1 to 50 g of precursor) by a route consisting of two parallel and two sequential chemical reactions. The isomers were characterized by 1H NMR, 13C NMR, nuclear Overhauser enhancement spectroscopy NMR, melting temperature, and melting enthalpy. For each isomer, the Hansen solubility parameters and the radius of its solubility sphere were experimentally determined by solubility tests in 15 common solvents and two solvent blends. The solubility of each isomer in pressurized CO2 was determined at 30 and 50 °C from 72.2 to 112.9 bar, by an in situ high-pressure spectrometry technique, which was validated with the anthracene-CO2 system. The solubility of both isomers in CO2 increased with pressure in the range of temperatures and pressures considered, but that of collinin exhibited an asymptotic behavior around 80.8 and 104.8 bar, at 30 and 50 °C, respectively.
- Pardo-Casta?o, Camilo,García, Andrés C.,Benavides, Paola,Bola?os, Gustavo
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p. 3799 - 3810
(2019/09/30)
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- Catalyst Behavior in Metal-Catalyzed Carbonyl-Olefin Metathesis
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Iron(III)-catalyzed carbonyl-olefin ring-closing metathesis employs reactivity not typically observed in Lewis acid-catalyzed reactions. In converting a ketone with a pendant olefin into a cycloalkene and a simple carbonyl byproduct, the reaction requires the Lewis acid catalyst to differentiate between the carbonyl of the substrate and that of the byproduct. It is necessary to determine how this solution interaction imparts the desired reactivity to best employ this method. Herein, we report detailed kinetic, spectroscopic, and colligative measurements applied toward the identification of the solution structures of the active Fe(III) and Ga(III) carbonyl-olefin metathesis catalysts. These data are consistent with formation of Lewis acid-carbonyl pairs for both metal systems under stoichiometric conditions. However, they diverge in the presence of higher equivalents of carbonyl, with Fe(III) forming highly ligated complexes, and no observed change for Ga(III). These findings are consistent with the resting state identity of the Fe(III) metathesis catalyst changing over the course of the reaction.
- Hanson, Carly S.,Psaltakis, Mary C.,Cortes, Janiel J.,Devery, James J.
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supporting information
p. 11870 - 11880
(2019/08/20)
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- PROCESS OF VITAMIN K2 DERIVATIVES PREPARATION
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Provided is an improved process of vitamin K2 derivatives preparation, represented by formula (I) wherein n is an integer from 3 to 13.
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Page/Page column 24; 25
(2019/10/29)
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- Exploiting the Synthetic Potential of Sesquiterpene Cyclases for Generating Unnatural Terpenoids
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The substrate flexibility of eight purified sesquiterpene cyclases was evaluated using six new heteroatom-modified farnesyl pyrophosphates, and the formation of six new heteroatom-modified macrocyclic and tricyclic sesquiterpenoids is described. GC-O analysis revealed that tricyclic tetrahydrofuran exhibits an ethereal, peppery, and camphor-like olfactoric scent.
- Oberhauser, Clara,Harms, Vanessa,Seidel, Katja,Schr?der, Benjamin,Ekramzadeh, Kimia,Beutel, Sascha,Winkler, Sven,Lauterbach, Lukas,Dickschat, Jeroen S.,Kirschning, Andreas
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supporting information
p. 11802 - 11806
(2018/09/10)
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- Domino Aryne Annulation via a Nucleophilic-Ene Process
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1,2-Benzdiyne equivalents possess the unique property that they can react with two arynophiles through iteratively generated 1,2- and 2,3-aryne intermediates. Upon rational modification on the second leaving group of these aryne precursors, a domino aryne annulation approach was developed through a nucleophilic-ene reaction sequence. Various benzo-fused N-heterocyclic frameworks were achievable under transition metal-free conditions with a broad substrate scope.
- Xu, Hai,He, Jia,Shi, Jiarong,Tan, Liang,Qiu, Dachuan,Luo, Xiaohua,Li, Yang
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supporting information
p. 3555 - 3559
(2018/03/21)
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- Transition-Metal-Free Formylation of Allylzinc Reagents Leading to α-Quaternary Aldehydes
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The first example of formylation of allylzinc reagents using S-phenyl thioformate is presented. The reaction proceeded under mild conditions without any transition-metal catalyst, forming quaternary carbon centers with reactive functionalities, such as formyl and vinyl groups. Moreover, Barbier-type formylation of an allylic bromide with a sterically demanding thioformate was achieved. As a preliminary result, asymmetric formylation was conducted using a menthol-derived chiral thioformate.
- Haraguchi, Ryosuke,Kusakabe, Akinori,Mizutani, Nakaba,Fukuzawa, Shin-Ichi
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supporting information
p. 1613 - 1616
(2018/03/23)
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- Squalene-Hopene Cyclase: On the Polycyclization Reactions of Squalene Analogues Bearing Ethyl Groups at Positions C-6, C-10, C-15, and C-19
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Squalene-hopene cyclase (SHC) has been found to convert acyclic squalene into 6,6,6,6,5-fused pentacyclic triterpenes hopene and hopanol. The enzymatic reactions of squalene analogues bearing ethyl groups in lieu of methyl groups at positions C-6, C-10, C-15, and C-19 have been examined to investigate whether the larger ethyl substituents (a C1 unit increment) are accepted as substrates and to investigate how these substitutions affect polycyclization cascades. Analogue 6-ethylsqualene 19a did not cyclize, which indicates that substitution with the bulky group at C-6 completely inhibited the polycyclization reaction. In contrast, 19-ethylsqualene 19b afforded a wide spectrum of cyclization products, including mono-, bi-, tetra-, and pentacyclic products in a ratio of 6:6:1:2. The production of tetra- and pentacyclic scaffolds suggests that the reaction cavity for D-ring formation site is somewhat loosely packed and can accept the 19-ethyl group, and that a robust hydrophobic interaction exists between the 19-ethyl group and the binding site. In contrast to 19b, 10-ethylsqualene 20a and 15-ethylsqualene 20b afforded mainly mono- and bicyclic products, that is, the polycyclization cascade terminated prematurely at the bicyclic reaction stage. Therefore, the catalytic domains for the 10- and 15-methyl binding sites are tightly packed and cannot fully accommodate the Et substituents. The cyclization pathways followed by the ethyl-substituted substrates in the presence of SHC and lanosterol and β-amyrin synthases are compared.
- Takahashi, Kazunari,Sasaki, Yusuke,Hoshino, Tsutomu
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supporting information
p. 1477 - 1490
(2018/04/06)
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- Propene as an Atom-Economical Linchpin for Concise Total Synthesis of Polyenes: Piericidin A
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A concise and convergent total synthesis of piericidin A is disclosed. The synthesis hinges on the utilization of propene as a synthetic linchpin to merge the properly elaborated alkyne fragments, leading to the 1,3,6-triene motif of piericidin A. Utilization of propene as a unique alkene, capable of sequential coupling with two alkynes, is further illustrated in the context of various 1,3,6-triene products. The latter process proceeds with high atom economy and efficiently gives rise to complex frameworks from readily accessible alkyne substrates. This strategic C-C bond formation offers an orthogonal paradigm in the design of synthetic routes, leading to higher step economy and more efficient syntheses of polyunsaturated natural products.
- Trost, Barry M.,Gholami, Hadi
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supporting information
p. 11623 - 11626
(2018/09/21)
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- Nucleophilic Substitutions of Alcohols in High Levels of Catalytic Efficiency
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A practical method for the nucleophilic substitution (SN) of alcohols furnishing alkyl chlorides, bromides, and iodides under stereochemical inversion in high catalytic efficacy is introduced. The fusion of diethylcyclopropenone as a simple Lewis base organocatalyst and benzoyl chloride as a reagent allows notable turnover numbers up to 100. Moreover, the use of plain acetyl chloride as a stoichiometric promotor in an invertive SN-type transformation is demonstrated for the first time. The operationally straightforward protocol exhibits high levels of stereoselectivity and scalability and tolerates a variety of functional groups.
- Stach, Tanja,Dr?ger, Julia,Huy, Peter H.
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supporting information
p. 2980 - 2983
(2018/05/28)
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- Photoreductive Removal of O-Benzyl Groups from Oxyarene N-Heterocycles Assisted by O-Pyridine-pyridone Tautomerism
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Facile photoreductive protocols have been developed to remove benzyl O-protective groups from oxyarene N-heterocycles at positions capable for 2-/4-O-pyridine-2-/4-pyridone tautomerism. Blue light irradiation, a [Ru] or [Ir] photocatalyst, and ascorbic acid in a water-acetonitrile solution debenzylates a variety of aryl N-heterocycles cleanly and selectively. Ascorbic acid has two functions in the reaction. On the one hand, it protonates the N-heterocycles that reduces their reduction potentials notably and on the other hand it acts as a sacrificial reductant. Reduction potentials and free energy barriers calculated at the CPCM-B3LYP/6-31+G? level can predict the reactivities of the studied substrates.
- Todorov, Aleksandar R.,Wirtanen, Tom,Helaja, Juho
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p. 13756 - 13767
(2017/12/26)
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- β-Amyrin Biosynthesis: Effect of Steric Bulk at the 6-, 10- and 15-Positions in the 2,3-Oxidosqualene Backbone on Polycyclisation Cascades
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β-Amyrin synthase incubation experiments have been conducted to determine the influence of steric effects at the 6-, 10- and 15-positions of 2,3-oxidosqualene on the polycyclisation pathway. Nor- and ethyl-substituted oxidosqualene analogues were synthesised. Cyclisation of the ethyl-substituted analogues did not occur, but the nor analogues underwent a polycyclisation cascade to yield fully cyclised products with 6/6/6/6/6-fused pentacyclic scaffolds generated via a final oleanyl cation. Previously, we reported that 19- and 23-ethyl-substituted analogues underwent polycyclisation reactions. Therefore, the catalytic domain involved in earlier cyclisation steps is notably compact. In contrast, the catalytic domain in the later cyclisation steps is more loosely packed (less compact) to accommodate the bulky ethyl group. The reaction cavities for recognising branched methyl groups are discussed by comparing β-amyrin synthase with other triterpene cyclases such as lanosterol and hopene synthases.
- Terasawa, Yuri,Sasaki, Yusuke,Yamaguchi, Yuki,Takahashi, Kazunari,Hoshino, Tsutomu
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supporting information
p. 287 - 295
(2017/01/24)
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- Anti-influenza activity of monoterpene-containing substituted coumarins
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Compounds simultaneously carrying the monoterpene and coumarin moieties have been tested for cytotoxicity and inhibition of activity against influenza virus A/California/07/09 (H1N1)pdm09. The structure of substituents in the coumarin framework, as well as the structure and the absolute configuration of the monoterpenoid moiety, are shown to significantly influence the anti-influenza activity and cytotoxicity of the compounds under study. The compounds with a bicyclic pinane framework exhibit the highest selectivity indices (the ratios between the cytotoxicity and the active dose). The derivative of (?)-myrtenol 15c, which is characterized by promising activity, low cytotoxicity, and synthetic accessibility, has the greatest potential among this group of compounds. It exhibited the highest activity when added to the infected cell culture at early stages of viral reproduction.
- Khomenko, Tatyana M.,Zarubaev, Vladimir V.,Orshanskaya, Iana R.,Kadyrova, Renata A.,Sannikova, Victoria A.,Korchagina, Dina V.,Volcho, Konstantin P.,Salakhutdinov, Nariman F.
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supporting information
p. 2920 - 2925
(2017/06/01)
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- Forging C-C Bonds with Hindered Nucleophiles and Carbonyl Electrophiles: Reactivity and Selectivity of Allylic Tin Reagents/n-BuLi
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Under activation with n-BuLi, trialkylstannanes containing crotyl-, geranyl-, and phenyldienylmethyl appendages were reacted with efficiency and selectivity to various ketone and enone electrophiles with low reactivity. The straightforward process gives access to tertiary alcohols that are vicinal to quaternary carbons. With α,α′-dimethoxy-γ-pyrone, on the other hand, the grafting of a dienyl side chain was effected to prepare dienyl α′-methoxy-γ-pyrone in a stereo- and regioselective and convergent manner. Furthermore, the advantages of this route were highlighted for the preparation of organolithium species at low temperature with the formation of a minimum amount of salts. Synthetic manipulations were demonstrated to illustrate the potential of the chemistry for constructing acyclic and cyclic terpene scaffolds.
- Cormier, Morgan,Ahmad, Maha,Maddaluno, Jacques,De Paolis, Micha?l
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p. 4920 - 4927
(2018/02/07)
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- A detailed view on 1,8-cineol biosynthesis by Streptomyces clavuligerus
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The stereochemical course of the cyclisation reaction catalysed by the bacterial 1,8-cineol synthase from Streptomyces clavuligerus was investigated using stereospecifically deuterated substrates. In contrast to the well investigated plant enzyme from Salvia officinalis, the reaction proceeds via (S)-linalyl diphosphate and the (S)-terpinyl cation, while the final cyclisation reaction is in both cases a syn addition, as could be shown by incubation of (2-13C)geranyl diphosphate in deuterium oxide.
- Rinkel, Jan,Rabe, Patrick,Zur Horst, Laura,Dickschat, Jeroen S.
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supporting information
p. 2317 - 2324
(2016/11/17)
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- METHOD OF CONVERTING ALCOHOL TO HALIDE
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The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
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Page/Page column 182; 183; 184
(2017/01/02)
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- Geranyl Geranyl Acetone Analogs and Uses Thereof
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The invention relates to novel therapeutic compounds, more in particular to biologically active analogs and uses thereof as medicament, for instance for the treatment of atrial fibrillation. Provided is a compound of the general formula (formula I) wherein R1 is H or a saturated or unsaturated aliphatic moiety comprising 1 to 8 C-atoms; and X is selected from the group consisting of moieties X1, X2, X3, X4, X5 and X6. Exemplary uses include the prevention or therapeutic treatment of a HSF1-mediated disease.
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Paragraph 0072
(2015/06/10)
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- N-GLYCOSYLATION OF PEPTIDES AND PROTEINS
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A process for the production of a glycoconjugate by N-glycosylation of a protein or peptide comprising the sequence D/E-X-N-X-S/T, wherein each X is the same or different and is any natural amino acid other than proline, wherein the process comprises reacting the protein or peptide with a polyisoprenyl pyrophosphate of formula (I), or a salt thereof, in the presence of PglB: (I) to produce the glycoconjugate comprising the protein or peptide having a saccharide [SI] linked to the asparagine in the sequence D/E-X-N-X-S/T. Polyisoprenylpyrophosphates used as substrates in the biocatalytic process are also provided, as well as certain glycoconjugates.
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Page/Page column 17
(2015/05/05)
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- Conformational Analysis, Thermal Rearrangement, and EI-MS Fragmentation Mechanism of (1(10)E,4E,6S,7R)-Germacradien-6-ol by 13C-Labeling Experiments
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An uncharacterized terpene cyclase from Streptomyces pratensis was identified as (+)-(1(10)E,4E,6S,7R)-germacradien-6-ol synthase. The enzyme product exists as two interconvertible conformers, resulting in complex NMR spectra. For the complete assignment of NMR data, all fifteen (13C1)FPP isotopomers (FPP=farnesyl diphosphate) and (13C15)FPP were synthesized and enzymatically converted. The products were analyzed using various NMR techniques, including 13C, 13C COSY experiments. The (13C)FPP isotopomers were also used to investigate the thermal rearrangement and EI fragmentation of the enzyme product. All 15 isotopomers of (13C1)- and fully labeled (13C15)farnesyl diphosphate were synthesized and converted to the title compound by a newly characterized bacterial terpene cyclase from Streptomyces pratensis. The enzyme products were used for structure elucidation of the sesquiterpene alcohol, full assignment of NMR data and a conformational analysis, and investigation of its Cope rearrangement and of its EI-MS fragmentation mechanism.
- Rabe, Patrick,Barra, Lena,Rinkel, Jan,Riclea, Ramona,Citron, Christian A.,Klapschinski, Tim A.,Janusko, Aron,Dickschat, Jeroen S.
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supporting information
p. 13448 - 13451
(2015/11/09)
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- Organic Photocatalytic Cyclization of Polyenes: A Visible-Light-Mediated Radical Cascade Approach
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A visible-light-mediated, organic photocatalytic stereoselective radical cascade cyclization of polyprenoids is described. The desired cascade cyclization products are achieved in good yields and high stereoselectivities with eosinY as photocatalyst in hexafluoro-2-propanol. The catalyst system is also suitable for 1,3-dicarbonyl compounds, which require only catalytic amounts of LiBr to promote the formation of the corresponding enols.
- Yang, Zhongbo,Li, Han,Zhang, Long,Zhang, Ming-Tian,Cheng, Jin-Pei,Luo, Sanzhong
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supporting information
p. 14723 - 14727
(2015/10/19)
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- Gold nanoparticles decorated with mannose-6-phosphate analogues
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Herein, the preparation of neoglycoconjugates bearing mannose-6-phosphate analogues is described by: (a) synthesis of a cyclic sulfate precursor to access the carbohydrate head-group by nucleophilic displacement with an appropriate nucleophile; (b) introduction of spacers on the mannose-6-phosphate analogues via Huisgen's cycloaddition, the Julia reaction, or the thiol-ene reaction under ultrasound activation. With the resulting compounds in hand, gold nanoparticles could be functionalized with various carbohydrate derivatives (glycoconjugates) and then tested for angiogenic activity. It was observed that the length and flexibility of the spacer separating the sugar analogue from the nanoparticle have little influence on the biological response. One particular nanoparticle system substantially inhibits blood vessel growth in contrast to activation by the corresponding monomeric glycoconjugate, thereby demonstrating the importance of multivalency in angiogenic activity.
- Combemale, Stephanie,Assam-Evoung, Jean-Norbert,Houaidji, Sabrina,Bibi, Rashda,Barragan-Montero, Veronique
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p. 1120 - 1149
(2014/02/14)
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- First total synthesis of a guanidine alkaloid Nitensidine D using immobilized ionic liquid, microwaves and formamidinesulfinic acid
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An efficient first total synthesis of a naturally occurring guanidine alkaloid, Nitensidine D isolated from ethanol extract of Pterogyne nitens has been described. Geraniol has been used as the starting material. N-alkylation of phthalimide has been achieved using immobilized ionic liquid and formamidinesulfinic acid acts as the guanylating reagent. [Figure not available: see fulltext.]
- Shallu,Sharma,Singh, Jasvinder
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p. 1869 - 1874
(2015/02/05)
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- Synthesis and bioactivity of diketopiperazine PJ147 and its derivatives from Gliocladium sp. YUP08
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Concise total synthesis of diketopiperazine PJ147, obtained from mycelium of Gliocladium sp. YUP08, has been achieved in seven steps with 43.5% overall yield. Biological evaluation of PJ147 exhibited strong inhibiting activity against A375-S2, Hela, P388, A-549, HL-60, and BEL-7420 cell lines. Thus, eight derivatives of PJ147 with high water solubility were also synthesized to facilitate the in vivo bioassay of this kind of diketopiperazines. 2014
- Li, Xue-Zheng,Chen, Gang,Wang, Hai-Feng,Hua, Hui-Ming,Pei, Yue-Hu
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p. 764 - 769
(2014/08/18)
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- Rationally designed short polyisoprenol-linked PglB substrates for engineered polypeptide and protein N-glycosylation
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The lipid carrier specificity of the protein N-glycosylation enzyme C. jejuni PglB was tested using a logical, synthetic array of natural and unnatural C10, C20, C30, and C40 polyisoprenol sugar pyrophosphates, including those bearing repeating cis-prenyl units. Unusual, short, synthetically accessible C20 prenols (nerylnerol 1d and geranylnerol 1e) were shown to be effective lipid carriers for PglB sugar substrates. Kinetic analyses for PglB revealed clear KM-only modulation with lipid chain length, thereby implicating successful in vitro application at appropriate concentrations. This was confirmed by optimized, efficient in vitro synthesis allowing >90% of Asn-linked β-N-GlcNAc-ylated peptide and proteins. This reveals a simple, flexible biocatalytic method for glycoconjugate synthesis using PglB N-glycosylation machinery and varied chemically synthesized glycosylation donor precursors.
- Liu, Feng,Vijayakrishnan, Balakumar,Faridmoayer, Amirreza,Taylor, Thomas A.,Parsons, Thomas B.,Bernardes, Goncalo J.L.,Kowarik, Michael,Davis, Benjamin G.
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supporting information
p. 566 - 569
(2014/02/14)
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- GERANYL GERANYL ACETONE ANALOGS AND USES THEREOF
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Title: Geranyl geranyl acetone analogs and uses thereof. Abstract The invention relates to novel therapeutic compounds, more in particular to biologically active analogs and uses thereof as medicament, for instance for the treatment of atrial fibrillation. Provided is a compound of the general formula wherein R1 is H or a saturated or unsaturated aliphatic moiety comprising 1 to 8 C- atoms; and X is selected from the group consisting of moieties X1, X2, X3, X4, X5 and X6. Exemplary uses include the prevention or therapeutic treatment of a HSF1-mediated disease.
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Page/Page column 18
(2013/11/05)
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- GERANYL GERANYL ACETONE ANALOGS AND USES THEREOF
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The invention relates to novel therapeutic compounds, more in particular to biologically active analogs and uses thereof as medicament, for instance for the treatment of atrial fibrillation. Provided is a compound of the general formula (formula I) wherein R1 is H or a saturated or unsaturated aliphatic moiety comprising 1 to 8 C- atoms; and X is selected from the group consisting of moieties X1, X2, X3, X4, X5 and X6. Exemplary uses include the prevention or therapeutic treatment of a HSF1-mediated disease.
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Page/Page column 20
(2013/11/05)
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- Design, synthesis and anticancer activity evaluation of diazepinomicin derivatives
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A series of diazepinomicin derivatives were synthesized and evaluated in vitro for their growth inhibitory activity against the human carcinoma cell lines. The results indicated the anticancer selectivity of this kind of compounds. Based on the results, preliminary structure-activity relationships were discussed.
- Yu, Yongguo,Wu, Jianbo,Lei, Fan,Chen, Lei,Wan, Weili,Hai, Li,Guan, Mei,Wu, Yong
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p. 369 - 373
(2013/07/26)
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- Synthesis of isoprenoid chain-contained chemical probes for an investigation of molecular interactions by using quartz crystal microbalance
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Five probes including four that contained isoprenoid chain were synthesized. These probes were assembled onto the gold-coated quartz crystal chips for analysis of their interactions with four yeast proteins by using the quartz crystal microbalance technology. Results showed that 3-phosphoglycerate phosphokinase and triosephosphate isomerase had clear interactions with certain probes, while glutathione reductase and phosphoglucose isomerase gave much lower interaction signals. It also suggested that 3-phosphoglycerate phosphokinase had two sites interacting with the probe attached with a geranyl moiety. Further molecule simulation experiments provided supportive information on these intermolecular interactions. Together, our data suggested that there are hydrophobic interactions, with relatively good selectivity, between isoprenoid chain and proteins.
- Liu, Wujun,Zhang, Yixin,Hou, Shuhua,Zhao, Zongbao Kent
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supporting information
p. 6208 - 6210
(2013/10/22)
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- A convergent stereocontrolled synthesis of [3-14C]solanesol
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In this communication, we report the synthesis of 5 mCi of [3- 14C]solanesol (1) prepared from ethyl [3-14C]acetoacetate and (all-E)-octaprenyl bromide (2) in four steps, with a specific radioactivity of 19.83 mCi/mmol and with a chemical/ stereochemical and radiochemical purity of ≥ 95%. (Figure 1). Position 3 of the chain was selected for 14C labelling because of the metabolic stability of this position. Unlabelled (all-E)-octaprenyl (18) (Scheme 4) necessary for this work was prepared via a convergent iterative 'allyl-allyl' coupling approach of precursors easily derived from readily available inexpensive starting materials. Copyright
- Roe, Stephen J.,Oldfield, Mark F.,Geach, Neil,Baxter, Andrew
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p. 485 - 491
(2014/03/21)
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