- Purification and characterization of a novel extracellular lipase catalyzing hydrolysis of oleyl benzoate from Acinetobacter nov. sp. strain KM109.
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A new lipase (OBase) which efficiently hydrolyzes oleyl benzoate (OB) was found in the culture supernatant of Acinetobacter nov. sp. strain KM109, a new isolate growing in a minimum medium containing OB as the sole carbon source. OBase was purified to homogeneity with 213-fold purification and 0.8% yield. The molecular weight was estimated to be 62,000 +/- 1,000 by SDS-PAGE under denatured-reduced conditions and to be 50,000 +/- 1,000 by gel-filtration HPLC under native conditions; these findings indicate that OBase is a monomeric enzyme. The optimum temperature and pH of OBase were about 45 degrees C and pH 8. Temperature and pH stabilities were at or lower than 35 degrees C and in a range of pH 6-8, respectively. Purified OBase preferentially hydrolyzed p-nitrophenyl benzoate (pNPB) over p-nitrophenyl acetate (pNPA) or p-nitrophenyl caproate (pNPC) [pNPB/pNPA = 20 and pNPB/pNPC = 5.4], indicating that OBase has a high affinity for benzoyl esters. Partial amino-acid sequences of OBase fragments obtained after lysyl endopeptidase treatment showed no similarity with known proteins.
- Mitsuhashi,Yamashita,Hwan,Ihara,Nihira,Yamada
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Read Online
- Tuning the Thermo-Sensitivity of Micellar Systems through a Blending Approach
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This paper reports an original and easy route toward thermosensitive micelles based on a lipidic core and with adjustable cloud point temperatures (TCP) through a simple blending approach between two copolymers of different TCP. The cationic ring-opening polymerization (CROP) of various 2-alkyl-2-oxazoline monomers was first investigated from both mesylated and tosylated lipoinitiators and different lipid-b-poly(2-methyl-2-oxazoline), lipid-b-poly(2-ethyl-2-oxazoline), lipid-b-poly(2-isopropyl-2-oxazoline) and lipid-b-poly((2-ethyl-2-oxazoline)-co-(2-isopropyl-2-oxazoline)) copolymers were synthesized. Blending of lipid-b-p(EtOx) and lipid-b-p(iPrOx) copolymers in various proportions were then prepared and their TCP investigated through UV-visible spectroscopy. Very interesting results were obtained as the blends exhibit a single TCP ranging from 35 to 45 °C. Furthermore, the blends TCP correspond to those of the statistical lipid-b-p((EtOx)-co-(iPrOx)) for the same p(EtOx)/p(iPrOx) content up to 52 wt % of p(EtOx). The blending approach is then an attractive strategy to control the TCP of micellar systems through a simple and easy formulation approach rather than fastidious syntheses.
- El Asmar, Arlette,Gimello, Olinda,Morandi, Ga?lle,Le Cerf, Didier,Lapinte, Vincent,Burel, Fabrice
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Read Online
- Synthesis of pH-sensitive micelles from linseed oil using atom transfer radical polymerisation (ATRP)
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This paper reports the synthesis of an amphiphilic copolymer from linseed oils and its successive auto-association in water into pH-sensitive micelles. An original ATRP lipoinitiator is first designed from linseed oil in two steps. tert-butyl acrylate (tBA) polymerization is consequently initiated from this original initiator and amphiphilic copolymers are obtained after subsequent acidolysis of the PtBA block into poly(acrylic acid) (PAA). The ability of a lipid-b-PAA copolymer to auto-associate in water is finally investigated through different techniques (Fluorescence, Surface Tension, QELS). This copolymer forms well-defined micelles in acidic media with a low critical micellar concentration (cmc) of 7.6 mg L-1 and dissociates when the pH is raised above 7.
- Hespel, Louise,Kaifas, Elise,Lecamp, Laurence,Picton, Luc,Morandi, Ga?lle,Burel, Fabrice
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- SYNTHESIS OF MUSCALURE - THE PHEROMONE OF Musca domestica
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A method for obtaining cis-tricos-9-ene (muscalure) - the pheromone of the housefly - from the readily available ethyl oleate has been developed.
- Verba, G. G.,Abdukakharov, V. S.,Abduvakhabov, A. A.
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Read Online
- Balancing the efficacy vs. the toxicity of promiscuous natural products: Paclitaxel-based acid-labile lipophilic prodrugs as promising chemotherapeutics
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TumorSelect is an anticancer technology that combines cytotoxics, nanotechnology, and knowledge of human physiology to develop innovative therapeutic interventions with minimal undesirable side effects commonly observed in conventional chemotherapy. Tumors have a voracious appetite for cholesterol which facilitates tumor growth and fuels their proliferation. We have transformed this need into a stealth delivery system to disguise and deliver anticancer drugs with the assistance of both the human body and the tumor cell. Several designer prodrugs are incorporated within pseudo-LDL nanoparticles, which carry them to tumor tissues, are taken up, internalized, transformed into active drugs, and inhibit cancer cell proliferation. Highly lipophilic prodrug conjugates of paclitaxel suitable for incorporation into the pseudo-LDL nanoparticles of the TumorSelect delivery vehicle formulation were designed, synthesized, and evaluated in the panel of 24-h NCI-60 human tumor cell line screening to demonstrate the power of such an innovative approach. Taxane prodrugs, viz., ART-207 was synthesized by tethering paclitaxel to lipid moiety with the aid of a racemic solketal as a linker in cost-effective, simple, and straightforward synthetic transformations. In addition to the typical 24-h NCI screening protocol, these compounds were assessed for growth inhibition or killing of ovarian cell lines for 48 and 72h-time intervals and identified the long-lasting effectiveness of these lipophilic prodrugs. All possible, enantiomerically pure isomers of ART-207 were also synthesized, and cytotoxicities were biosimilar to racemic ART-207, suggesting that enantiopurity of linker has a negligible effect on cell proliferation. To substantiate further, ART-207 was evaluated for its in vivo tumor reduction efficacy by studying the xenograft model of ovarian cancer grown in SCID mice. Reduced weight loss (a measure of toxicity) in the ART-207 group was observed, even though it was dosed at 2.5x the paclitaxel equivalent of Abraxane. As a result, our delineated approach is anticipated to improve patient quality of life, patient retention in treatment regimes, post-treatment rapid recovery, and overall patient compliance without compromising the efficacy of the cytotoxic promiscuous natural products.
- Chittiboyina, Amar G.,Claudio, Pier Paolo,Haider, Saqlain,McChesney, James D.,Penfornis, Patrice
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- OLEIC ACID DERIVATIVES AS TREATMENTS FOR FRIEDREICH ATAXIA AND INHIBITORS OF FERROPTOSIS
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The invention relates to compounds of Formula I or Formula II: to compositions comprising such compounds, and to methods of use thereof for treating neurdegenerative disorders, such as Friedreich ataxia.
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- SYNTHESIS OF PHEROMONE DERIVATIVES VIA Z-SELECTIVE OLEFIN METATHESIS
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Disclosed herein are methods for synthesizing fatty olefin metathesis products of high Z-isomeric purity from olefin feedstocks of low Z-isomeric purity. The methods include contacting a contacting an olefin metathesis reaction partner, such as acylated alkenol or an alkenal acetal, with an internal olefin in the presence of a Z-selective metathesis catalyst to form the fatty olefin metathesis product. In various embodiments, the fatty olefin metathesis products are insect pheromones. Pheromone compositions and methods of using them are also described.
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Paragraph 0218
(2021/12/28)
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- Enantiomeric synthesis of natural alkylglycerols and their antibacterial and antibiofilm activities
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Alkylglycerols (AKGs) are bioactive natural compounds that vary by alkyl chain length and degree of unsaturation, and their absolute configuration is 2S. Three AKGs (5l–5n) were synthesised in enantiomerically pure form, and were characterised for the first time together with 12 other known and naturally occurring AKGs (5a–5k, 5o). Their structures were established using 1H and 13C APT NMR with 2D-NMR, ESI-MS or HRESI-MS and optical rotation data, and they were tested for their antibacterial and antibiofilm activities. AKGs 5a–5m and 5o showed activity against five clinical isolates and P. aeruginosa ATCC 15442, with MIC values in the range of 15–125 μg/mL. In addition, at half of the MIC, most of the AKGs reduced S. aureus biofilm formation in the range of 23%–99% and P. aeruginosa ATCC 15442 biofilm formation in the range of 14%–64%. The antibiofilm activity of the AKGs assessed in this work had not previously been studied.
- Fernández Montoya, Deicy J.,Contreras Jordan, Luis A.,Moreno-Murillo, Bárbara,Silva-Gómez, Edelberto,Mayorga-Wandurraga, Humberto
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supporting information
p. 2544 - 2550
(2019/11/13)
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- A Facile and Efficient Method for the Synthesis of Labeled and Unlabeled Very Long Chain Polyunsaturated Fatty Acids
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Several methods are available for elongation of fatty acid acyl chains. The present paper describes adaptation to the fatty acid field of a previously published protocol for manganese-based Wurtz type coupling of alkyl bromides. 22-Bromo-3(Z),6(Z),9(Z),12(Z),15(Z),18(Z)-docosahexaene, easily prepared from 4(Z),7(Z),10(Z),13(Z),16(Z),19(Z)-docosahexaenoic acid, was coupled to homologous ω-bromoesters by stirring for 4 hours at 40°C in the presence of manganese powder, a nickel catalyst and terpyridine. This afforded in yields of 70–75% a series of ω3-hexaenoates of chain lengths of 32–40 carbons. The corresponding fatty acids of >98% purity were obtained following saponification and final purification. By using methyl [2,2,3,3,4,4-2H6]10-bromodecanoate as coupling partner it was possible to prepare a very long chain fatty acid in isotopically labeled form, i.e., [2,2,3,3,4,4-2H6]14(Z),17(Z),20(Z),23(Z),26(Z),29(Z)-dotriacontahexaenoic acid. Also prepared were the monounsaturated long chain fatty acids 15(Z)-octadecenoic acid and 15(Z)-tetracosenoic acid. Very long chain fatty acids have been isolated from retina and other tissues and are of biological relevance. The methodology described will assist in further analytical and biological studies in this field.
- Hamberg, Mats
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p. 489 - 494
(2021/04/19)
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- Hydrosilylation of Esters Catalyzed by Bisphosphine Manganese(I) Complex: Selective Transformation of Esters to Alcohols
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Selective and efficient hydrosilylations of esters to alcohols by a well-defined manganese(I) complex with a commercially available bisphosphine ligand are described. These reactions are easy alternatives for stoichiometric hydride reduction or hydrogenation, and employing cheap, abundant, and nonprecious metal is attractive. The hydrosilylations were performed at 100 °C under solvent-free conditions with low catalyst loading. A large variety of aromatic, aliphatic, and cyclic esters bearing different functional groups were selectively converted into the corresponding alcohols in good yields.
- Bagh, Bidraha,Behera, Rakesh R.,Ghosh, Rahul,Khamari, Subrat,Panda, Surajit
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supporting information
p. 3642 - 3648
(2020/04/20)
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- Design and synthesis of amphiphilic 2-hydroxybenzylphosphonium salts with antimicrobial and antitumor dual action
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Here we report the synthesis and biological evaluation of a series of new 2-hydroxybenzylphosphonium salts (QPS) with antimicrobial and antitumor dual action. The most active compounds exhibit antimicrobial activity at a micromolar level against Gram-positive bacteria Sa (ATCC 209p and clinical isolates), Bc (1–2 μM) and fungi Tm and Ca, and induced no notable hemolysis at MIC. The change in nature of substituents of the same length led to a drastic change of biological activity. Self-assembly behavior of the octadecyl and oleyl derivatives was studied. QPS demonstrated self-assembly within the micromolar range with the formation of nanosized aggregates capable of the solubilizing hydrophobic probe. The synthesized phosphonium salts were tested for cytotoxicity. The most potent salt was active against on M?Hela cell line with IC50 on the level of doxorubicin and good selectivity. According to the cytofluorimetry analysis, the salts induced mitochondria-dependent apoptosis.
- Lyubina, Anna P.,Mironov, Vladimir F.,Pashirova, Tatiana N.,Sapunova, Anastasiia S.,Shaihutdinova, Zukhra M.,Tatarinov, Dmitry A.,Terekhova, Natalia V.,Voloshina, Alexandra D.,Zakharova, Lucia Ya.
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supporting information
(2020/05/19)
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- Manganese-catalysed transfer hydrogenation of esters
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Manganese catalysed ester reduction using ethanol as a hydrogen transfer agent in place of dihydrogen is reported. High yields can be achieved for a range of substrates using 1 mol% of a Mn(i) catalyst, with an alkoxide promoter. The catalyst is derived from a tridentate P,N,N ligand.
- Oates, Conor L.,Widegren, Magnus B.,Clarke, Matthew L.
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supporting information
p. 8635 - 8638
(2020/08/21)
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- Diaminodiphosphine tetradentate ligand and ruthenium complex thereof, and preparation methods and applications of ligand and complex
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The invention discloses a diaminodiphosphine tetradentate ligand and a ruthenium complex thereof, and preparation methods and applications of the ligand and the complex, and provides a ruthenium complex represented by a formula I, wherein L is a diaminodiphosphine tetradentate ligand represented by a formula II, and X and Y are respectively and independently chlorine ion, bromine ion, iodine ion,hydrogen negative ion or BH4. According to the present invention, the ruthenium complex exhibits excellent catalytic activity in the catalytic hydrogenation reactions of ester compounds, has high yield and high chemical selectivity, is compatible with conjugated and non-conjugated carbon-carbon double bond, carbon-carbon triple bond, epoxy, halogen, carbonyl and other functional groups, and hasgreat application prospects.
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Paragraph 0307-0310
(2019/11/04)
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- Method for preparing fatty alcohols with same carbon number by catalytic hydrodeoxygenation from fatty acid and/or fatty acid ester
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The invention provides a method for preparing fatty alcohols with the same carbon number by catalytic hydrodeoxygenation from fatty acid and/or fatty acid ester. The method comprises the following step: in a reaction vessel, carrying out hydrodeoxygenation reaction on the fatty acid and/or fatty acid ester and hydrogen in the presence of a catalyst at a low temperature of 100-240 DEG C and under alow hydrogen pressure of 0.1-5 MPa to obtain desired fatty alcohol products with the same carbon number. According to the invention, the fatty alcohols with the same carbon number is prepared from the fatty acid and/or fatty acid ester through an active metal modified MeaXbAlc composite catalyst as defined herein. The method has the advantages of high conversion rate, good selectivity, mild reaction conditions, stable catalyst and the like, and has quite good industrial application prospect.
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Paragraph 0060; 0061; 0062; 0067; 0068
(2019/05/08)
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- OLEIC ACID DERIVATIVES, PHARMACEUTICAL COMPOSITION OR FOOD COMPOSITION COMPRISING SAID OLEIC ACID DERIVATIVES, AND THEIR USES
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This invention relates to oleic acid derivative comprising a hydrophobic part C17H33 linked to a particular polar head part "A", especially for use as a medicament, for instance, for the treatment of a disorder caused by the GPR120 receptor and/or the CD36 receptor, comprising administering to a subject in need thereof a therapeutically effective amount of said oleic acid derivative or of said pharmaceutical composition. The invention also relates to the use of said oleic acid derivative as a food composition.
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Page/Page column 36-37
(2019/12/25)
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- Selective Hydroboration of Carboxylic Acids with a Homogeneous Manganese Catalyst
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Catalytic reduction of carboxylic acid to the corresponding alcohol is a challenging task of great importance for the production of a variety of value-added chemicals. Herein, a manganese-catalyzed chemoselective hydroboration of carboxylic acids has been developed with a high turnover number (>99?000) and turnover frequency (>2000 h-1) at 25 °C. This method displayed tolerance of electronically and sterically differentiated substrates with high chemoselectivity. Importantly, aliphatic long-chain fatty acids, including biomass-derived compounds, can efficiently be reduced. Mechanistic studies revealed that the reaction occurs through the formation of active manganese-hydride species via an insertion and bond metathesis type mechanism.
- Barman, Milan K.,Das, Kuhali,Maji, Biplab
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p. 1570 - 1579
(2019/01/30)
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- Novel clamp metal complex and application thereof
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The invention discloses a method for preparing a novel clamp-shaped complex and application of the novel clamp-shaped complex in the reaction of catalytic hydrogenation of carboxylic acid ester compounds to produce corresponding alcohols and reaction of carbon dioxide catalytic hydrogenation to form formamide compounds. Carboxylic acid esters and hydrogen as raw materials or carbon dioxide, hydrogen and amine compounds as raw materials are reacted in an organic solvent condition or a solvent-free condition in the presence of a transition metal complex as a catalyst to respectively form the corresponding alcohol compounds and/or corresponding formamide compounds. The method has the advantages of being high in reaction efficiency, good in selectivity, mild in conditions, economical, environmentally-friendly, and simple in operation, and has good promotion and application prospects.
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Paragraph 0410-0412; 0450-0453; 0519-0522
(2019/04/26)
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- Method used for reduction of tertiary amide into alcohols and/or amines
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The invention discloses a method used for reduction of tertiary amide into alcohols and/or amines. The method comprises following steps: tertiary amide, an alkali metal reagent, and a proton donor agent are added into an organic solvent for a following reaction selectively: when the proton donor agent is a raw material alcohol and/or inorganic salt aqueous solution, the reaction product is an alcohol compound and/or tertiary amine compound. The method is capable of realizing selective reduction of tertiary amide into alcohols and tertiary amine compounds, the yield is high, the suitable rangeis wide, operation is safe and simple, the adopted raw materials are cheap and easily available; no precious metal catalyst, toxic silanes, and flammable and combustible metal hydrides are adopted; notoxic by product is generated; reaction is more friendly to the environment; problems in the prior art that amide compound reducing method operation is complex, conditions are strict, and control ofproducts is difficult are solved.
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Paragraph 0215-0218
(2019/08/07)
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- Selective Hydrogenation of Carboxylic Acids to Alcohols or Alkanes Employing a Heterogeneous Catalyst
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The chemoselective hydrogenation of carboxylic acids to either alcohols or alkanes is reported, employing a heterogeneous bimetallic catalyst consisting of rhenium and palladium supported on graphite. α-Chiral carboxylic acids were hydrogenated without loss of optical purity. The catalyst displays a reverse order of reactivity upon hydrogenation of different carboxylic functions with esters being less reactive than amides and carboxylic acids. This allows for chemoselective hydrogenation of an acid in the presence of an ester or an amide function.
- Ullrich, Johannes,Breit, Bernhard
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p. 785 - 789
(2018/02/14)
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- At Long Last: Olefin Metathesis Macrocyclization at High Concentration
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Macrocyclic lactones, ketones, and ethers can be obtained in the High-Concentration Ring-Closing Metathesis (HC-RCM) reaction in high yield and selectivity at concentrations 40 to 380 times higher than those typically used by organic chemists for similar macrocyclizations. The new method consists of using tailored ruthenium catalysts together with applying vacuum to distill off the macrocyclic product as it is formed by the metathetical backbiting of oligomers. Unlike classical RCM, no large quantities of organic solvents are used, but rather inexpensive nonvolatile diluents, such as natural or synthetic paraffin oils. Moreover, use of a protecting atmosphere or a glovebox is not needed, as the new catalysts are perfectly moisture and air stable. In addition, some other cyclic compounds previously reported as unobtainable by RCM in neat conditions, or in high dilutions even, can be formed with the help of the HC-RCM method.
- Sytniczuk, Adrian,Dabrowski, Micha?,Banach, ?ukasz,Urban, Mateusz,Czarnocka-?niada?a, Sylwia,Milewski, Mariusz,Kajetanowicz, Anna,Grela, Karol
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supporting information
p. 8895 - 8901
(2018/07/05)
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- Bio-based primary amine cationic surfactant and preparation method thereof
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The invention discloses a bio-based primary amine cationic surfactant and a preparation method thereof, and belongs to the technical field of surfactant science and application. The synthesis of the surfactant comprises the following steps that oleic acid and methyl alcohol are used as raw materials for sequentially carrying out esterification, reduction and substitution, so that oleyl alcohol issybthesized; substitution is carried out on the oleyl alcohol and 3-hydroxybenzaldehyde, and substitution, reduction, acidification reaction are carried out, so that the final bio-based primary aminecationic surfactant is obtained. The bio-based primary amine cationic surfactant has wide raw material sources, is biologically renewable, is green and environmentally friendly, and has high biodegradability, the types of biological-based surfactants with renewable resources as raw materials are enriched, and the bio-based primary amine cationic surfactant can be widely applied to research of a surfactant self-organizing system.
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- Elongation of the Hydrophobic Chain as a Molecular Switch: Discovery of Capsaicin Derivatives and Endogenous Lipids as Potent Transient Receptor Potential Vanilloid Channel 2 Antagonists
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The transient receptor potential vanilloid type-2 (TRPV2) protein is a nonselective Ca2+ permeable channel member of the TRPV subfamily, still considered an orphan TRP channel due to the scarcity of available selective and potent pharmacological tools and endogenous modulators. Here we describe the discovery of novel synthetic long-chain capsaicin derivatives as potent TRPV2 antagonists in comparison to the totally inactive capsaicin, the role of their hydrophobic chain, and how the structure-activity relationships of such derivatives led, through a ligand-based approach, to the identification of endogenous long-chain fatty acid ethanolamides or primary amides acting as TRPV2 antagonists. Both synthetic and endogenous antagonists exhibited differential inhibition against known TRPV2 agonists characterized by distinct kinetic profiles. These findings represent the first example of both synthetic and naturally occurring TRPV2 modulators with efficacy in the submicromolar/low-micromolar range, which will be useful for clarifying the physiopathological roles of this receptor, its regulation, and its targeting in pathological conditions.
- Schiano Moriello, Aniello,López Chinarro, Silvia,Novo Fernández, Olalla,Eras, Jordi,Amodeo, Pietro,Canela-Garayoa, Ramon,Vitale, Rosa Maria,Di Marzo, Vincenzo,De Petrocellis, Luciano
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p. 8255 - 8281
(2018/09/25)
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- Inexpensive Ruthenium NNS-Complexes as Efficient Ester Hydrogenation Catalysts with High C=O vs. C=C Selectivities
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Ru(NNS)(PPh3)Cl2 (NNS=2-(methylthio)-N-(pyridin-2-yl-methyl)ethan-1-amine) was employed in the hydrogenation of α,β-unsaturated esters, reaching selectivities for the allylic alcohol up to 95% in the hydrogenation of iso-butylcinnamate. In addition, several ester substrates were hydrogenated with catalyst loadings as low as 0.05?mol%. Surprisingly, selectivity of the hydrogenation of the C=O vs the C=C bonds strongly depends on the solvent. (Figure presented.).
- Stadler, Bernhard M.,Puylaert, Pim,Diekamp, Justus,van Heck, Richard,Fan, Yuting,Spannenberg, Anke,Hinze, Sandra,de Vries, Johannes G.
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supporting information
p. 1151 - 1158
(2018/02/06)
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- Reduction and Reductive Deuteration of Tertiary Amides Mediated by Sodium Dispersions with Distinct Proton Donor-Dependent Chemoselectivity
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A practical and scalable single electron transfer reduction mediated by sodium dispersions has been developed for the reduction and reductive deuteration of tertiary amides. The chemoselectivity of this method highly depends on the nature of the proton donor. The challenging reduction via C-N bond cleavage has been achieved using Na/EtOH, affording alcohol products, while the use of Na/NaOH/H2O leads to the formation of amines via selective C-O scission. Sodium dispersions with high specific surface areas are crucial to obtain high yields and good chemoselectivity. This new method tolerates a range of tertiary amides. Moreover, the corresponding reductive deuterations mediated by Na/EtOD-d1 and Na/NaOH/D2O afford useful α,α-dideuterio alcohols and α,α-dideuterio amines with an excellent deuterium content.
- Zhang, Bin,Li, Hengzhao,Ding, Yuxuan,Yan, Yuhao,An, Jie
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p. 6006 - 6014
(2018/05/24)
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- Identification of in situ flower volatiles from kiwifruit (Actinidia chinensis var. deliciosa) cultivars and their male pollenisers in a New Zealand orchard
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In situ flower volatiles from six kiwifruit cultivars (Actinidia chinensis var. deliciosa); ‘Hayward’, ‘Chieftain’, ‘M56’, ‘Zes007’ (Green11), ‘M36’, and ‘M43’ were collected by dynamic headspace sampling. Forty-five compounds were detected in the headspace of the flowers, with straight chain hydrocarbons and terpenes accounting for >98% of the volatiles emitted quantitatively across the six cultivars. Of these hydrocarbons, (3Z,6Z,9Z)-heptadecatriene is reported for the first time from a floral source while (8Z)-hexadecene and (9Z)-nonadecene are reported for the first time from kiwifruit flowers. All three hydrocarbons were verified by synthesis. Quantitative comparison of the six honey bee perceived compounds from the headspace of the cultivars showed that the males ‘M36’ and ‘M43’ closely matched the female cultivar Green11 that they are used to pollinate. Males ‘M56’ and ‘Chieftain’ were not as closely matched to the female cultivar ‘Hayward’ that they are used to pollinate. The male ‘M56’ in particular differed significantly from the female ‘Hayward’ in four of the six honey bee perceived compounds.
- Twidle, Andrew M.,Suckling, David M.,Seal, Alan G.,Fedrizzi, Bruno,Pilkington, Lisa I.,Barker, David
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- Non-Pincer-Type Manganese Complexes as Efficient Catalysts for the Hydrogenation of Esters
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Catalytic hydrogenation of carboxylic acid esters is essential for the green production of pharmaceuticals, fragrances, and fine chemicals. Herein, we report the efficient hydrogenation of esters with manganese catalysts based on simple bidentate aminophosphine ligands. Monoligated Mn PN complexes are particularly active for the conversion of esters into the corresponding alcohols at Mn concentrations as low as 0.2 mol % in the presence of sub-stoichiometric amounts of KOtBu base.
- van Putten, Robbert,Uslamin, Evgeny A.,Garbe, Marcel,Liu, Chong,Gonzalez-de-Castro, Angela,Lutz, Martin,Junge, Kathrin,Hensen, Emiel J. M.,Beller, Matthias,Lefort, Laurent,Pidko, Evgeny A.
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supporting information
p. 7531 - 7534
(2017/06/13)
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- Solvent- and base-free synthesis of wax esters from fatty acid methyl esters by consecutive one-pot, two-step catalysis
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The one-pot, two-step synthesis of wax esters was successfully conducted by consecutive homogeneous ruthenium-catalysed hydrogenation-dehydrogenation reactions of fatty acid methyl esters, in the absence of solvent and of base additive. Under optimized conditions, excellent conversion and selectivity were reached. Furthermore, physicochemical investigations revealed that the resulting compounds display properties similar to benchmark commercial products extracted from natural sources of lesser availability compared to the herein considered bioresources, making this chemical route very promising regarding further potential industrial implementation.
- Nguyen,Raffa,Morin,Desset,Capet,Nardello-Rataj,Dumeignil,Gauvin
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supporting information
p. 5665 - 5673
(2017/12/06)
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- Mechanistic insights into catalytic carboxylic ester hydrogenation with cooperative Ru(II)-bis{1,2,3-triazolylidene}pyridine pincer complexes
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Transmetallation of newly designed lutidine-based CNC or CNN ligands L, featuring flanking 1,2,3-triazolylidene (tzNHCs) moieties, from Ag(I) to Ru(II) provided access to well-defined cationic [RuII(CO)(H)(L)(PPh3)]+ complexes 2 and 5. Spectroscopic investigations confirm that, in both complexes, the tridentate ligand binds in a rare facial mode to the metal center. The complexes, that exhibit ligand-based reversible deprotonation/dearomatization reactivity, are active in catalytic ester hydrogenation in the presence of KOtBu (≥20 mol%) as an exogenous base. The beneficial effect of the base on catalytic activity relates to transesterification of substrates to the corresponding tert-butyl ester derivatives, which are hydrogenated considerably faster than methyl esters. The mechanistic findings in this work confirm that this transformation is very complex, with this transesterification, metal-ligand cooperative reactivity, base strength and possibly product inhibition all playing a role. Furthermore, relevant Ru(CNC)(hydride) species have been observed by NMR spectroscopy under near-catalytic conditions.
- Sluijter, Soraya N.,Korstanje, Ties J.,van der Vlugt, Jarl Ivar,Elsevier, Cornelis J.
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supporting information
p. 30 - 37
(2017/07/22)
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- Long-chain α-ω Diols from renewable fatty acids via tandem olefin metathesis-ester hydrogenation
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Long chain α-ω diols were readily accessed from renewable fatty acid methyl esters following an orthogonal tandem self-metathesis-ester hydrogenation protocol. By adding a base and a bidentate ligand, the metathesis catalysts were transformed in situ into efficient ester hydrogenation catalysts. The selectivity of the hydrogenation reaction was tuned towards the exclusive formation of either the unsaturated or the saturated diol by modifying the ligand/catalyst ratio. An orthogonal tandem cross-metathesis-ester hydrogenation reaction was also applied for the synthesis of a fragrance compound.
- Gonzalez-De-Castro, Angela,Cosimi, Elena,Aguila, Mae Joanne B.,Gajewski, Piotr,Schmitkamp, Mike,De Vries, Johannes G.,Lefort, Laurent
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supporting information
p. 1678 - 1684
(2017/06/07)
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- Hydrogenation of Esters to Alcohols Catalyzed by Defined Manganese Pincer Complexes
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The first manganese-catalyzed hydrogenation of esters to alcohols has been developed. The combination of Mn(CO)5Br with [HN(CH2CH2P(Et)2)2] leads to a mixture of cationic and neutral Mn PNP pincer complexes, which enable the reduction of various ester substrates, including aromatic and aliphatic esters as well as diesters and lactones. Notably, related pincer complexes with isopropyl or cyclohexyl substituents showed very low activity.
- Elangovan, Saravanakumar,Garbe, Marcel,Jiao, Haijun,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
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supporting information
p. 15364 - 15368
(2016/12/03)
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- Method For Synthesising Esters
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A method for synthesising a second ester from a first ester, the method including the following steps: a) placing a first ester and a catalyst in the presence of dihydrogen such as to obtain a first alcohol and a second alcohol; b) extracting the second alcohol from the reaction medium; c) reacting the first alcohol with the catalyst of step a) in order to obtain a second ester and dihydrogen; and d) recirculating the dihydrogen obtained in step c) by injecting same into step a).
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Paragraph 0071; 0072
(2016/10/27)
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- A General, Practical Triethylborane-Catalyzed Reduction of Carbonyl Functions to Alcohols
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A combination of the abundant and low-cost triethylborane and sodium alkoxide generates a highly efficient catalyst for reduction of esters, as well as ketones and aldehydes, to alcohols using an inexpensive hydrosilane under mild conditions. The catalyst system exhibits excellent chemoselectivity and a high level of functional group tolerance. Mechanistic studies revealed a resting state of sodium triethylalkoxylborate that is the product of the reaction of BEt3 with sodium alkoxide. This borate species reacts with hydrosilane to form NaBEt3H, which rapidly reduces esters.
- Peng, Dongjie,Zhang, Mintao,Huang, Zheng
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supporting information
p. 14737 - 14741
(2015/10/19)
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- Structure-activity relationships of lysophosphatidylserine analogs as agonists of G-protein-coupled receptors GPR34, P2Y10, and GPR174
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Lysophosphatidylserine (LysoPS) is an endogenous lipid mediator generated by hydrolysis of membrane phospholipid phosphatidylserine. Recent ligand screening of orphan G-protein-coupled receptors (GPCRs) identified two LysoPS-specific human GPCRs, namely, P2Y10 (LPS2) and GPR174 (LPS3), which, together with previously reported GPR34 (LPS1), comprise a LysoPS receptor family. Herein, we examined the structure-activity relationships of a series of synthetic LysoPS analogues toward these recently deorphanized LysoPS receptors, based on the idea that LysoPS can be regarded as consisting of distinct modules (fatty acid, glycerol, and l-serine) connected by phosphodiester and ester linkages. Starting from the endogenous ligand (1-oleoyl-LysoPS, 1), we optimized the structure of each module and the ester linkage. Accordingly, we identified some structural requirements of each module for potency and for receptor subtype selectivity. Further assembly of individually structure-optimized modules yielded a series of potent and LysoPS receptor subtype-selective agonists, particularly for P2Y10 and GPR174.
- Ikubo, Masaya,Inoue, Asuka,Nakamura, Sho,Jung, Sejin,Sayama, Misa,Otani, Yuko,Uwamizu, Akiharu,Suzuki, Keisuke,Kishi, Takayuki,Shuto, Akira,Ishiguro, Jun,Okudaira, Michiyo,Kano, Kuniyuki,Makide, Kumiko,Aoki, Junken,Ohwada, Tomohiko
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p. 4204 - 4219
(2015/06/08)
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- Highly efficient tetradentate ruthenium catalyst for ester reduction: Especially for hydrogenation of fatty acid esters
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A new tetradentate ruthenium complex has been developed for hydrogenation of esters. The catalysts structure features a pyridinemethanamino group and three tight chelating five-membered rings. The structure character is believed to be responsible for its high stability and high carbonylation-resistant properties. Thus, this catalyst shows outstanding performance in the catalytic hydrogenation of a variety of esters, especially for fatty acid esters, which may be used in practical applications. New insight on designing hydrogenation catalyst for reducing esters to alcohols has been provided through theoretical calculations.
- Tan, Xuefeng,Wang, Yan,Liu, Yuanhua,Wang, Fangyuan,Shi, Liyang,Lee, Ka-Ho,Lin, Zhenyang,Lv, Hui,Zhang, Xumu
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supporting information
p. 454 - 457
(2015/03/05)
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- Ru-Sn-B/Al2O3 catalysts for selective hydrogenation of methyl oleate: Influence of the Ru/Sn Ratio
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This study focuses on the influence of the Ru/Sn ratio on the catalytic hydrogenation of methyl oleate to oleyl alcohol using Ru-Sn-B catalysts, notably on the catalytic activity and selectivity. Sn addition acts positively over the oleyl selectivity by reducing the rates of C=O and C=C saturation but also decreases the global activity. The catalyst with the highest activity and selectivity towards oleyl alcohol is Ru(1%)-Sn(2%)-B/Al2O3. At a low Sn loading (0.5%) the catalyst has high activity for hydrogenation of the carbonyl group and the carbon-carbon double bond. As a consequence stearyl alcohol is produced with high yield. At a high Sn content (4%) the catalyst has lower selectivity to oleyl alcohol due to its low capacity for hydrogenating the carbonyl group. However it has enough activity for hydrogenating the C=C double bonds to produce the saturated methyl ester.
- Sánchez, María A.,Mazzieri, Vanina A.,Vicerich, María A.,Vera, Carlos R.,Pieck, Carlos L.
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- COMPLEX CATALYSTS BASED ON AMINO-PHOSPHINE LIGANDS FOR HYDROGENATION AND DEHYDROGENATION PROCESSES
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The present application discloses novel PWNN and PWNWP metal catalysts for organic chemical syntheses including hydrogenation (reduction) of unsaturated compounds or dehydrogenation of substrates. The range of hydrogenation substrate compounds includes esters, lactones, enals, enones, enolates, oils and fats, resulting in alcohols, enols, diols, and triols as reaction products. The catalysts of current application can be used to catalyze a hydrogenation reaction under solvent free conditions. The present catalysts also allow the hydrogenation to proceed without added base, and it can be used in place of the conventional reduction methods employing hydrides of the main-group elements. Furthermore, the catalysts of the present application can catalyze a dehydrogenation reaction under homogenous and/or acceptorless conditions. As such, the catalysts provided herein can be useful in substantially reducing cost and improving the environmental profile of manufacturing processes for a variety of chemicals.
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Page/Page column 39; 40; 41; 42
(2014/09/29)
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- Evaluating a sodium dispersion reagent for the Bouveault-Blanc reduction of esters
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A new sodium dispersion reagent has been evaluated for the reduction of esters. Na-D15, a sodium dispersion with sodium particle size of 5-15 μm, is a nonpyrophoric reagent that can be handled in air. In this study, a broad range of aliphatic ester substrates were reduced to primary alcohols by Na-D15/i-PrOH with good yields. The method compares favorably with modern metal hydride reductions and is much safer and efficient than the traditional Bouveault-Blanc reduction.
- An, Jie,Work, D. Neil,Kenyon, Craig,Procter, David J.
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p. 6743 - 6747
(2014/08/05)
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- Influence of the operating conditions and kinetic analysis of the selective hydrogenation of oleic acid on Ru-Sn-B/Al2O3 catalysts
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The influence of the operating conditions on the selectivity and activity of Ru-Sn-B/Al2O3 catalysts for the hydrogenation of oleic acid to oleyl alcohol was studied. It was found that the Ru-Sn-B/Al 2O3 catalyst is selective to oleyl alcohol while Ru or Ru-B/Al2O3 catalysts are not selective to produce oleyl alcohol. The electronic and catalytic properties of Ru are modified by the strong interaction between Sn and B. The incorporation of Sn leads to catalysts capable of producing oleyl alcohol. The experiments of oleic acid hydrogenation showed that an increase in reaction temperature leads to an increase in activity while the selectivity to oleyl alcohol goes through a maximum. This is because the reactions of hydrogenation of CC double bond have lower activation energies than hydrogenolytic reactions. The increase in operating pressure has a positive effect on conversion and a more important effect on selectivity. A very simple first order kinetic model is proposed and reasonably represents the results obtained. This model can be useful to compare catalyst performance more rationally.
- Sánchez, María A.,Pouilloux, Yannick,Mazzieri, Vanina A.,Pieck, Carlos L.
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p. 552 - 558
(2013/09/23)
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- Electron transfer reduction of carboxylic acids using SmI 2-H2O-Et3N
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The first general method for efficient electron transfer reduction of carboxylic acids has been developed. The protocol using SmI2 - H 2O - Et3N allows for reduction of a variety of carboxylic acids in excellent yields and provides an attractive alternative to processes mediated by reactive alkali metals, lithium aluminum hydride, and boron hydrides. Of broader significance, the method allows acyl radical equivalents to be generated from carboxylic acids under mild reaction conditions.
- Szostak, Michal,Spain, Malcolm,Procter, David J.
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supporting information; experimental part
p. 840 - 843
(2012/04/11)
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- Synthesis of (Z)-(2′R)-1-O-(2′-methoxynonadec-10′-enyl)- sn-glycerol, a new analog of bioactive ether lipids
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An unsaturated 2-methoxy-substituted 1-O-alkylglycerol, (Z)-(2′R)-1-O-(2′-methoxynonadec-10′-enyl)-sn-glycerol, a new analog of bioactive ether lipids, was synthesized from oleic acid and 2,3-isopropylidene-sn-glycerol. The two key steps of this synthesis were the conversion of oleyl aldehyde to a monounsaturated epoxide using Matteson's method followed by hydrolytic kinetic resolution and a nucleophilic epoxide opening by 2,3-isopropylidene-sn-glycerol in the presence of potassium tert-butoxide in anhydrous DMF, which appeared to be a good reagent for this purpose. Furthermore, the diol by-product of the HKR process was also easily converted back to the starting epoxide thus almost doubling the amount of target molecule.
- Pemha, René,Pegnyemb, Dieudonné Emmanuel,Mosset, Paul
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experimental part
p. 2973 - 2983
(2012/06/01)
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- Selective switchable iron-catalyzed hydrosilylation of carboxylic acids
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Selective reduction of carboxylic acids either to aldehydes or alcohols is achieved using a one pot procedure based on iron-catalyzed hydrosilylations. Using phenylsilane and (COD)Fe(CO)3 catalyst under UV-irradiation at rt, alcohols were obtained specifically in good yields, whereas aldehydes were selectively obtained using TMDS and (t-PBO)Fe(CO)3 catalyst under thermal activation.
- Misal Castro, Luis C.,Li, Haoquan,Sortais, Jean-Baptiste,Darcel, Christophe
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supporting information
p. 10514 - 10516,3
(2020/09/02)
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- Copper(II) triflate-catalyzed reduction of carboxylic acids to alcohols and reductive etherification of carbonyl compounds
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A protocol is described for the reduction of carboxylic acids to primary alcohols using 1,1,3,3-tetramethyldisiloxane (TMDS) and a catalytic amount of Cu(OTf)2. Aliphatic as well as aromatic carboxylic acids are reduced in high selectivity and good yields. TMDS/Cu(OTf)2 has also been found to be an efficient catalytic reducing system for the preparation of symmetrical ethers from carbonyl compounds under mild conditions.
- Zhang, Yin-Jie,Dayoub, Wissam,Chen, Guo-Rong,Lemaire, Marc
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experimental part
p. 7400 - 7407
(2012/09/10)
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- Iron-catalyzed hydrosilylation of esters
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The first hydrosilylation of esters catalyzed by a well defined iron complex has been developed. Esters are converted to the corresponding alcohols at 100 °C, under solvent-free conditions and visible light activation. Copyright
- Bezier, David,Venkanna, Gopaladasu T.,Castro, Luis C. Misal,Zheng, Jianxia,Roisnel, Thierry,Sortais, Jean-Baptiste,Darcel, Christophe
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supporting information; experimental part
p. 1879 - 1884
(2012/09/22)
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- From esters to alcohols and back with ruthenium and osmium catalysts
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There and back again: Hydrogenation of esters and the reverse reaction of dehydrogenative coupling of alcohols are efficiently catalyzed by dimeric complexes of Ru and Os under neutral conditions. The Os dimer (see picture) is an outstanding catalyst for the hydrogenation of alkenoates and triglycerides, and allows production of fatty alcohols from olive oil. This complex converts ethanol into ethyl acetate and hydrogen under reflux. Copyright
- Spasyuk, Denis,Smith, Samantha,Gusev, Dmitry G.
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supporting information; experimental part
p. 2772 - 2775
(2012/05/20)
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- Zinc-catalyzed chemoselective reduction of esters to alcohols
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Economical alcohols! A general and chemoselective catalytic reduction of esters to alcohols using inexpensive zinc acetate and silanes has been developed. The operational simplicity and the high functional group tolerance, without the need for protecting and deprotecting steps, make this procedure particularly attractive for organic synthesis. Copyright
- Das, Shoubhik,Moeller, Konstanze,Junge, Kathrin,Beller, Matthias
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experimental part
p. 7414 - 7417
(2011/08/05)
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- Synthesis and characterization of degradable multivalent cationic lipids with disulfide-bond spacers for gene delivery
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Gene therapy provides powerful new approaches to curing a large variety of diseases, which are being explored in ongoing worldwide clinical trials. To overcome the limitations of viral gene delivery systems, synthetic nonviral vectors such as cationic liposomes (CLs) are desirable. However, improvements of their efficiency at reduced toxicity and a better understanding of their mechanism of action are required. We present the efficient synthesis of a series of degradable multivalent cationic lipids (CMVLn, n = 2 to 5) containing a disulfide bond spacer between headgroup and lipophilic tails. This spacer is designed to be cleaved in the reducing milieu of the cytoplasm and thus decrease lipid toxicity. Small angle X-ray scattering demonstrates that the initially formed lamellar phase of CMVLn-DNA complexes completely disappears when reducing agents such as DTT or the biologically relevant reducing peptide glutathione are added to mimic the intracellular milieu. The CMVLs (n = 3 to 5) exhibit reduced cytotoxicity and transfect mammalian cells with efficiencies comparable to those of highly efficient non-degradable analogs and benchmark commercial reagents such as Lipofectamine 2000. Thus, our results demonstrate that degradable disulfide spacers may be used to reduce the cytotoxicity of synthetic nonviral gene delivery carriers without compromising their transfection efficiency.
- Shirazi, Rahau S.,Ewert, Kai K.,Leal, Cecilia,Majzoub, Ramsey N.,Bouxsein, Nathan F.,Safinya, Cyrus R.
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experimental part
p. 2156 - 2166
(2012/06/15)
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- InBr3-catalyzed deoxygenation of carboxylic acids with a hydrosilane: Reductive conversion of aliphatic or aromatic carboxylic acids to primary alcohols or diphenylmethanes
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A simple and practical procedure for the direct reduction of aliphatic carboxylic acids with a variety of functional groups to a primary alcohol using the mild reducing reagent tetramethyldisiloxane (TMDS), in the presence of a catalytic amount of InBr3 has been developed. This simple reducing system, when used together with a hydrosilane, allows the preparation of the diphenylmethane derivative directly from an aromatic carboxylic acid and an aromatic compound. Copyright
- Sakai, Norio,Kawana, Keita,Ikeda, Reiko,Nakaike, Yumi,Konakahara, Takeo
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experimental part
p. 3178 - 3183
(2011/06/28)
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- COPOLYHYDROXYALKYLGLUTAMINES FUNCTIONALISED WITH HYDROPHOBIC GROUPS, AND USES THEREOF, ESPECIALLY IN THERAPEUTICS
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The invention relates to novel biodegradable materials which are based on modified polyamino acids and which can be used for the vectorisation of active principle(s) (AP). The invention also relates to novel pharmaceutical, cosmetic, dietary or phytosanitary compositions based on said polyamino acids. The aim of the invention is to provide a novel polymer raw material which can be used for the vectorisation of active principles and which can optimally fulfil all required specifications in said area, namely: biocompatibility, biodegradability and the ability to become easily associated with many active principles or to solubilise said principles and to release same in vivo. Said aim is achieved with novel copolyhydroxyalkylglutamines comprising glutamine units and optionally glutamate units and bearing hydrophobic groups containing between 8 and 30 carbon atoms. Said copolyhydroxyalkylglutamines are amphiphilic and can be easily and economically transformed into particles for the vectorisation of active principles, whereby said particles can form stable aqueous colloidal suspensions.
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- Reduction of aromatic and aliphatic esters using the reducing systems MoO2(acac)2 or V(O)(OiPr)3 in combination with 1,1,3,3-tetramethyldisiloxane
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An efficient reduction of aromatic and aliphatic esters with 1,1,3,3-tetramethyldisiloxane in combination with [MoO2(acac) 2] or [V(O)(OiPr)3] is reported. In the former system, the presence of triphenylphosphane oxide allows high conversion and good isolated yield to be reached. For the latter system, no ligand is necessary to obtain the corresponding alcohols with similar results. 1,1,3,3-Tetramethyldisiloxane in association with [MoO2(acac)2] or [V(O)(OiPr)3] was found to efficiently reduce aliphatic and aromatic esters. Copyright
- Pehlivan, Leyla,Metay, Estelle,Laval, Stephane,Dayoub, Wissam,Delbrayelle, Dominique,Mignani, Gerard,Lemaire, Marc
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experimental part
p. 7400 - 7406
(2012/01/06)
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- Synthesis of the sulfonated condensed polynuclear aromatic (S-COPNA) resins as strong protonic acids
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The mixture (PXG/PR=1.00) of pyrene (PR) and p-xylylene glycol (1,4-benzenedimethanol) (PXG) in the presence of 5 wt % of p-toluenesulfonic acid (TsOH) was heated at 140 °C for 45 min under nitrogen to give the highly viscous condensed polynuclear aromatic (COPNA) resin. It was converted into an infusible and insoluble solid by further heating at 300 °C for 1 h. The obtained material was treated with fuming sulfuric acid at 80 °C for 15 h under nitrogen to give the sulfonated COPNA resin. The similar acidic resin was prepared by the reaction of phenanthrene or naphthalene with PXG in the presence of TsOH followed by sulfonation. The performance of the sulfonated polymers as the strong protonic acids was evaluated.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Horaguchi, Takaaki
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experimental part
p. 1314 - 1319
(2011/04/15)
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- Polyglutamic Acids Functionalised by Histidine Derivatives and Hydrophobic Groups and the Uses Thereof, in Particular for Therapeutic Purposes
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The invention relates to novel biodegradable materials based on modified polyamino acids and suitable, in particular, for vectoring active substance(s) (AS). Said invention also relates to novel pharmaceutical, cosmetic, dietary or plant protective compositions which are based on said polyamino acids. The aim of said invention is to provide a novel polymer raw material usable for vectoring the AS and capable to optimally meet all specification in this area: biocompatibility, biodegradability, ability to become easily associated with many active substances or to solubilise them and to release said active substances in vivo. The aim is attained to 30 carbon atoms. Said polyglutamates modified by histidine derivatives are soluble with pH lower than 5 and are easily and economically convertible into active substance vectorization particles which are able to form stable aqueous colloidal suspensions. On the contrary, said modified polyglutamates are insoluble in water with a physiological pH (7.4), and thereby have to be precipitated on an injection site in the case of a subcutaneous injection.
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- Polyamino acids functionalized by hydrophobic grafts bearing an anionic charge and applications thereof, such as therapeutic applications
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The present invention relates to novel materials based on biodegradable polyamino acids that are useful especially for the vectorization of active principle(s) (AP). The invention further relates to novel pharmaceutical, cosmetic, dietetic or phytosanitary compositions based on these polyamino acids. The object of the invention is to provide a novel polymer starting material that is capable of being used for the vectorization of AP and makes it possible on the one hand to achieve high polymer/AP ratios, and on the other hand optimally to satisfy all the specifications required in the case in point: biocompatibility, biodegradability, ability to associate easily with numerous active principles or to solubilize them, and ability to release these active principles in vivo. This object is achieved by the present invention, which relates first and foremost to linear polyamino acids comprising aspartic units or glutamic units and having hydrophobic grafts comprising hydrophobic groups containing from 8 to 30 carbon atoms, at least one of these hydrophobic grafts having at least one anionic charge and/or one or more mutually identical or different ionizable groups each capable of giving rise to at least one anionic charge. These polymers are amphiphilic and anionic and are capable of being converted easily and economically to particles for the vectorization of active principles, these particles themselves being capable of forming stable aqueous colloidal suspensions.
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