- Solubility in CO2 and carbonation studies of epoxidized fatty acid diesters: Towards novel precursors for polyurethane synthesis
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Novel linear polyurethanes were synthesized by bulk polyaddition of diamines with two vegetable-based biscarbonates produced from oleic acid methyl ester. Internal carbonated fatty acid diester (ICFAD) and terminal carbonated fatty acid diester (TCFAD) were obtained by the reaction of their epoxide precursors with CO2. Terminal epoxy fatty acid diester (TEFAD) was found to be more soluble and more reactive in CO2 than internal epoxy fatty acid diester (IEFAD). Polyurethanes obtained by polyaddition of TCFAD and ICFAD with diamines exhibit molecular weights up to 13500 g mol-1 and glass transitions around -15 °C. Amide linkages were not observed when secondary diamine was used as the comonomer.
- Boyer, Aurelie,Cloutet, Eric,Tassaing, Thierry,Gadenne, Benoit,Alfos, Carine,Cramail, Henri
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Read Online
- Breaking and Making of Olefins Simultaneously Using Ozonolysis: Application to the Synthesis of Useful Building Blocks and Macrocyclic Core of Solomonamides
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(Figure Presented) A simple and practical one-pot, two-directional approach to access olefinic esters through simultaneous breaking and making of olefins using ozonolysis of alkenyl aryl selenides is disclosed. The scope of the method with a variety of examples is demonstrated, and the end products obtained here are useful building blocks. As a direct application of the present method, the macrocyclic core of potent anti-inflammatory natural cyclic peptides, solomonamides, is synthesized.
- Kashinath,Dhara, Santu,Reddy, D. Srinivasa
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Read Online
- Identification of novel decenoic acids in heated butter
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Novel decenoic acids such as (E)-4-decenoic acid and (E)- and (Z)-5-,6-decenoic acid were detected as minor components in heated butter using GC and GC/MS. The formation mechanism of these novel decenoic acids is discussed on the basis of the result of the reaction of δ-decalactone with active clay in a model experiment.
- Ito, Nobuhiko,Wada, Shigeru,Yamanaka, Yousuke,Takagaki, Hitoshi,Nakamura, Hironori
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Read Online
- ACYCLIC CARBENE LIGAND FOR RUTHENIUM COMPLEX FORMATION, RUTHENIUM COMPLEX CATALYST, AND USE THEREOF
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Provided are a novel acyclic carbene ligand for ruthenium complex formation; a ruthenium complex catalyst using the ligand; a method of using the complex as a catalyst in an ethylene-metathesis ethenolysis reaction; a method of preparing the ruthenium complex catalyst; and a method of preparing a linear alpha-olefin, the method including the step of reacting a linear or cyclic alkene compound in the presence of the ruthenium complex catalyst. The acyclic carbene ligand of the present invention and the ruthenium complex catalyst using the same have high selectivity and turnover number for terminal olefin formation in an ethylene-metathesis ethenolysis reaction, and thus linear α-olefins may be prepared with a high yield.
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Paragraph 0124-0130
(2021/05/14)
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- EXTRAHEPATIC DELIVERY
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One aspect of the present invention relates to a compound comprising an antisense strand which is complementary to a target gene; a sense strand which is complementary to said antisense strand; and one or more lipophilic monomers, containing one or more lipophilic moieties, conjugated to one or more positions on at least one strand, optionally via a linker or carrier. Another aspect of the invention relates to a method of gene silencing, comprising administering to a cell or a subject in need thereof a therapeutically effective amount of the lipophilic monomer-conjugated compound.
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Paragraph 0566; 0656
(2021/05/15)
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- Vortex Fluidic Ethenolysis, Integrating a Rapid Quench of Ruthenium Olefin Metathesis Catalysts
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Ruthenium-catalysed ethenolysis occurs in a vortex fluidic device (VFD)-a scalable, thin-film microfluidic continuous flow process. This process takes advantage of the efficient mass transfer of gaseous reagents into the dynamic thin film of liquid. Also reported is the rapid quenching of the ruthenium-based olefin metathesis catalyst by the addition of a saturated solution of N-acetyl-l-cysteine in MeCN, as a convenient alternative to previously reported quenching methods.
- Pye, Scott J.,Chalker, Justin M.,Raston, Colin L.
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p. 1138 - 1143
(2020/08/27)
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- Synthesis and Activity of Six-Membered Cyclic Alkyl Amino Carbene-Ruthenium Olefin Metathesis Catalysts
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Ru-cyclic alkyl amino carbene (Ru-CAAC) olefin metathesis catalysts perform extraordinarily in metathesis macrocyclization and ethenolysis, but previous studies have been limited to the use of five-membered CAAC (CAAC-5) ligands. In this work, we synthesized a different group of ruthenium catalysts with more σ-donating and π-accepting six-membered CAAC (CAAC-6) ligands, and their metathesis activity was probed through initiation studies, ring-closing metathesis (RCM), cross-metathesis, and ethenolysis. These catalysts display higher initiation rates than analogous Ru-CAAC-5 complexes but demonstrate lower activity in RCM and ethenolysis.
- Grubbs, Robert H.,Samkian, Adrian E.,Virgil, Scott C.,Xu, Yan,Yoon, Ki-Young
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supporting information
(2020/02/27)
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- TUNGSTEN IMIDO ALKYLIDENE O-BITET AND O-BINOL COMPLEXES AND USE THEREOF IN OLEFIN METATHESIS REACTIONS
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The invention relates to tungsten imido alkylidene compounds bearing a ligand derived from a 1,1'-binaphthyl-2-ol or a 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2- ol which bind to tungsten in its olate-form via proton abstraction from the phenolic OH group. The complexes may be used in various olefinic metathesis reactions, preferably ethenolysis and cross-metathesis of unsaturated fatty acid esters, and ring-closing metathesis reactions.
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Paragraph 00228-00232
(2020/12/11)
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- Direct and Tandem Routes for the Copolymerization of Ethylene with Polar Functionalized Internal Olefins
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Transition metal catalyzed ethylene copolymerization with polar monomers is a highly challenging reaction. After decades of research, the scope of suitable comonomer substrates has expanded from special to fundamental polar monomers and, recently, to 1,1-disubstituted ethylenes. Described in this contribution is a direct and tandem strategy to realize ethylene copolymerization with various 1,2-disubstituted ethylenes. The direct route is sensitive to sterics of both the comonomers and the catalyst. In the tandem route, ruthenium-catalyzed ethenolysis can convert 1,2-disubstituted ethylenes into terminal olefins, which can be subsequently copolymerized with ethylene to afford polar functionalized polyolefins. The one-pot, two-step tandem route is highly versatile and efficient in dealing with challenging substrates. This work is a step forward in terms of expanding the substrate scope for transition metal catalyzed ethylene copolymerization with polar-functionalized comonomers.
- Chen, Min,Chen, Changle
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supporting information
p. 1206 - 1210
(2019/12/24)
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- Cysteine-Targeted Insecticides against A. gambiae Acetylcholinesterase Are Neither Selective nor Reversible Inhibitors
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Acetylcholinesterase cysteine-targeted insecticides against malaria vector Anopheles gambia and other mosquitos have already been introduced. We have applied the olefin metathesis for the preparation of cysteine-targeted insecticides in high yields. The prepared compounds with either a succinimide or maleimide moiety were evaluated on Anopheles gambiae and human acetylcholinesterase with relatively high irreversible inhibition of both enzymes but poor selectivity. The concept of cysteine binding was not proved by several methods, and poor stability was observed of the chosen most potent/selective compounds in a water/buffer environment. Thus, our findings do not support the proposed concept of cysteine-targeted selective insecticides for the prepared series of succinimide or maleimide compounds.
- Gorecki, Lukas,Andrys, Rudolf,Schmidt, Monika,Kucera, Tomas,Psotka, Miroslav,Svobodova, Barbora,Hrabcova, Veronika,Hepnarova, Vendula,Bzonek, Petr,Jun, Daniel,Kuca, Kamil,Korabecny, Jan,Musilek, Kamil
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supporting information
p. 65 - 71
(2019/12/25)
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- Integrated extraction and catalytic upgrading of microalgae lipids in supercritical carbon dioxide
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Fatty acids from microalgae are attractive compounds for catalytic upgrading to chemicals, but their extraction often requires multi-step procedures and the use of various organic solvents. To relieve this bottleneck, we propose a straightforward approach of combined extraction and catalytic functionalization via olefin cross-metathesis (ethenolysis and butenolysis) in supercritical CO2 (scCO2). This is demonstrated for Phaeodactylum tricornutum microalgae biomass. ScCO2 at optimum conditions (90 °C, 620 atm, ρ(CO2) = 0.90 g mL-1) extracted the lipids selectively and quantitatively from previously disrupted cells, while organic solvent extraction for comparison additionally extracted polar diacylglycerides and chlorophylls. In a one-pot approach, olefin cross-metathesis of the unsaturated fatty acids (FA16:1, FA18:1 and FA20:5) by alkenolysis yielded the desirable mid-chain olefin and unsaturated ester products. The product spectrum compares to alkenolysis of individual model compounds in scCO2 as well as of separately scCO2 extracted microalgae oil. Both these ethenolysis and butenolysis proceed with conversions of more than 81% and high selectivities to the desired products. This biorefinery approach was further illustrated by the simultaneous extraction and catalytic isomerizing alkoxycarbonylation in scCO2.
- Zimmerer, Julia,Pingen, Dennis,Hess, Sandra K.,Koengeter, Tobias,Mecking, Stefan
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supporting information
p. 2428 - 2435
(2019/05/21)
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- IONIC METAL ALKYLIDENE COMPOUNDS AND USE THEREOF IN OLEFINIC METATHESIS REACTIONS
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A compound of formula (I) wherein: M is selected from Mo or W; X is selected from O or NR5; R1 and R2 are independently selected from H, C1-6 alkyl, and aryl; C1-6 alkyl and aryl optionally being substituted with one or more of C1-6 alkyl, C1-6 alkoxy, and O-C6H5; R3 is selected from a nitrogen-containing aromatic heterocycle being bound to M via said nitrogen; and from halogen; R4 is an aryl oxy group being bound to M via said oxygen of said aryl oxy group; wherein said aryl group Ar of said aryl oxy group is bound to a group Cat such to form a cationic ligand Cat+-Z-ArO-, wherein Z is either a covalent bond or a linker; R5 is alkyl or aryl, optionally substituted.
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Paragraph 00195; 00214
(2019/12/25)
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- Integrating Activity with Accessibility in Olefin Metathesis: An Unprecedentedly Reactive Ruthenium-Indenylidene Catalyst
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Access to leading olefin metathesis catalysts, including the Grubbs, Hoveyda, and Grela catalysts, ultimately rests on the nonscaleable transfer of a benzylidene ligand from an unstable, impure aryldiazomethane. The indenylidene ligand can be reliably installed, but to date yields much less reactive catalysts. A fast-initiating, dimeric indenylidene complex (Ru-1) is reported, which reconciles high activity with scaleable synthesis. Each Ru center in Ru-1 is stabilized by a state-of-the-art cyclic alkyl amino carbene (CAAC, C1) and a bridging chloride donor: the lability of the latter elevates the reactivity of Ru-1 to a level previously attainable only with benzylidene derivatives. Evaluation of initiation rate constants reveals that Ru-1 initiates >250× faster than indenylidene catalyst M2 (RuCl2(H2IMes)(PCy3)(Ind)), and 65× faster than UC (RuCl2(C1)2(Ind)). The slow initiation previously regarded as characteristic of indenylidene catalysts is hence due to low ligand lability, not inherently slow cycloaddition at the Ru=CRR′ site. In macrocyclization and "ethenolysis" of methyl oleate (i.e., transformation into α-olefins via cross-metathesis with C2H4), Ru-1 is comparable or superior to the corresponding, breakthrough CAAC-benzylidene catalyst. In ethenolysis, Ru-1 is 5× more robust to standard-grade (99.9%) C2H4 than the top-performing catalyst, probably reflecting steric protection at the quaternary CAAC carbon.
- Nascimento, Daniel L.,Gawin, Anna,Gawin, Rafa?,Guńka, Piotr A.,Zachara, Janusz,Skowerski, Krzysztof,Fogg, Deryn E.
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supporting information
p. 10626 - 10631
(2019/08/28)
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- Fluoro-imidazopyridinylidene Ruthenium Catalysts for Cross Metathesis with Ethylene
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A series of ruthenium metathesis catalysts bearing fluorinated imidazo[1,5-a]pyridin-3-ylidene carbenes (F-ImPy) were developed for ethenolysis (cross metathesis with ethylene) of methyl oleate. X-ray crystal structure analysis shows Ru-F interaction, and this fluorine substitution appears to be pivotal to have stable ImPy-Ru precatalysts. Ligand structure was varied for high catalyst activity and cross metathesis selectivity in ethenolysis reaction. F-ImPy-Ru catalysts showed high selectivity in ethenolysis of methyl oleate and thermal robustness under an ethylene atmosphere.
- Byun, Seunghwan,Seo, Huiyeong,Choi, Jun-Ho,Ryu, Ji Yeon,Lee, Junseong,Chung, Won-Jin,Hong, Sukwon
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supporting information
p. 4121 - 4132
(2019/10/16)
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- METATHESIS CATALYSTS
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This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.
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Paragraph 000118; 000119
(2018/03/09)
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- METHODS OF MAKING OLEFINIC E- AND Z-ISOMERS
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Method of making a second olefin using a first olefin, comprising steps (A) and (B): (A) performing a metathesis reaction with the first olefin in the presence of a metal complex configured to catalyse said metathesis reaction; (B) epoxidizing an olefin contained in the reaction mixture obtained in step (A) to form an epoxide; and deoxygenizing said epoxide to form said second olefin.
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Paragraph 00119; 00121
(2019/01/05)
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- USE OF RUTHENIUM COMPLEXES IN OLEFIN METATHESIS REACTION
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The invention relates to the use of ruthenium complexes, which are homogeneous catalysts and/or precatalysts of the olefin metathesis reaction, which lead to the production of alkenes containing an internal (non-terminal) double C=C bond.
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Page/Page column 18-19
(2018/05/27)
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- Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis
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The state-of-the-art in olefin metathesis is application of N-heterocyclic carbene (NHC)-containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)-containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported.
- Gawin, Rafa?,Kozakiewicz, Anna,Guńka, Piotr A.,D?browski, Pawe?,Skowerski, Krzysztof
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supporting information
p. 981 - 986
(2017/01/18)
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- Remarkably Efficient Microwave-Assisted Cross-Metathesis of Lipids under Solvent-Free Conditions
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Catalytic transformation of renewable feedstocks into fine chemicals is in high demands and olefin metathesis is a sophisticated tool for biomass conversion. Nevertheless, the large-scale viability of such processes depends on the conversion efficiency, energy efficiency, catalytic activity, selective conversion into desired products, and environmental footprint of the process. Therefore, conversions of renewables by using simple, swift, and efficient methods are desirable. A microwave-assisted ethenolysis and alkenolysis (using 1,5-hexadiene) of canola oil and methyl esters derived from canola oil (COME) and waste/recycled cooking oil (WOME) was carried out by using ruthenium-based catalytic systems. A systematic study using 1st and 2nd generation Grubbs and Hoveyda–Grubbs catalysts was carried out. Among all ruthenium catalysts, 2nd generation Hoveyda–Grubbs catalyst was found to be highly active in the range of 0.002–0.1 mol % loading. The conversions proved to be rapid providing unprecedented turnover frequencies (TOFs). High TOFs were achieved for ethenolysis of COME (21 450 min?1), direct ethenolysis of canola oil (19 110 min?1), for WOME (15 840 min?1) and for cross-metathesis of 1,5-hexadiene with COME (10 920 min?1). The ethenolysis of commercial methyl oleate was also performed with a TOF of 8000 min?1 under microwave conditions.
- Ullah, Aman,Arshad, Muhammad
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p. 2167 - 2174
(2017/05/26)
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- CATALYTIC ETHENOLYSIS OF OPTIONALLY-FUNCTIONALIZED INTERNAL UNSATURATED OLEFINS
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The invention relates to a process for obtaining alpha-olefins by heterogeneous catalytic ethenolysis of optionally-functionalized unsaturated, in particular mono- unsaturated, olefins. The invention also relates to new supported catalysts that can be used in the process of the invention and to a method for preparing said supported catalysts.
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Page/Page column 56-70
(2017/02/09)
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- GROUP 8 TRANSITION METAL CATALYSTS AND METHOD FOR MAKING SAME AND PROCESS FOR USE OF SAME IN OLEFIN DISPROPORTIONATION REACTIONS
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These catalyst compounds are represented by the formula (I and VI): wherein M is a Group 8 metal; X is an anionic ligand; L is a neutral two-electron donor ligand; A is a monotopic or ditopic chelating ligand. The present invention also relates to an easy applicable catalyst synthesis and the application in different olefin metathesis processes, e.g. Reaction Injection Molding (RIM), rotational molding, vacuum infusion, vacuum forming, process for conversion of fatty acids and fatty acid esters or mixtures thereof, in -olefins, dicarboxylic acids or dicarboxylic esters, etc.
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Page/Page column 57-58
(2017/12/09)
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- FRAGRANCE COMPOSITIONS COMPRISING COMPOUNDS WITH OLFACTORY QUALITIES
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The application relates to compositions comprising compounds of Formula I, Formula II, or Formula III and the use of these compositions in the fragrance industry, i.e., for the production of perfumes, air fresheners, laundry detergents, household cleaning products, liquid or bar soaps, shampoos, conditioners, hair sprays, cosmetics, deodorants, insect repellants, insecticides, and pet litter.
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Paragraph 00310; 00311
(2017/09/05)
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- Exploring the reactivity of a ruthenium complex in the metathesis of biorenewable feedstocks to generate value-added chemicals in memory of Professor the Lord Lewis of Newnham: Mentor, encourager, and Ph.D. advisor.
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Tricyclohexylphosphine[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][2-thienylmethylene]ruthenium(II) dichloride proves active for the ring-closing metathesis of linalool and citronellene, the self-metathesis of eugenol, and to some extent the ethenolysis of methyl oleate. Microwave heating and continuous-flow processing have been used as tools for performing the reactions. For the ring-closing metathesis reactions, transition from batch to flow processing for scale-up of the reaction is possible but it proves problematic in the case of cross-metathesis.
- Alexander, Kathryn A.,Paulhus, Emily A.,Lazarus, Gillian M.L.,Leadbeater, Nicholas E.
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- A chemoenzymatic route to chiral siloxanes
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An approach employing two enzymes—toluene dioxygenase and immobilized lipase B from Candida antarctica (N435)—was explored as a potential biocatalytic method for the coupling of chiral diols with siloxane species. Analysis of reaction mixtures using1H NMR spectroscopy suggested that up to 66% consumption of the siloxane starting materials had occurred. Oligomeric species were observed and chiral products from the coupling of a cyclic diol with a siloxane molecule were isolated and characterized by MALDI-ToF MS and GPC. Immobilized lipases from Rhizomucor miehei and Thermomyces lanuginosus were also explored as potential catalysts for the coupling reactions, however, their use only returned starting material.
- Naoum, Ravi,Séguin, Jacqueline P.,Trant, John F.,Frampton, Mark B.,Hudlicky, Tomá?,Zelisko, Paul M.
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supporting information
p. 4027 - 4031
(2016/07/06)
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- Cross metathesis of methyl oleate (MO) with terminal, internal olefins by ruthenium catalysts: Factors affecting the efficient MO conversion and the selectivity
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Cross metathesis (CM) reactions of methyl oleate (MO) with cis-4-octene (OC), cis-stilbene (CS) using RuCl2(PCy3)(IMesH2)(CHPh) [IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene; Cy = cyclohexyl] afforded CM products with high MO conversion and high selectivity under high molar (OC/MO, CS/MO) ratios; CM with cis-1,4-diacetoxy-2-butene also afforded metathesis products with high MO conversion under certain conditions. The efficient CM with allyltrimethylsilane proceeded with high activity, whereas the CM with glycidyl ether, β-pinene, and vanillylidenacetone proceeded with low MO conversion.
- Awang, Nor Wahida,Tsutsumi, Ken,Hu?táková, Barbora,Yusoff, Siti Fairus M.,Nomura, Kotohiro,Yamin, Bohari M.
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p. 100925 - 100930
(2016/11/09)
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- METHOD FOR PRODUCING OMEGA-HYDROXY FATTY ACID ESTER AND PRECURSOR COMPOUND THEREOF
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Provided is a method for producing a compound represented by Formula (III) while the production of by-products due to, for example, dimerization of a raw material or isomerization of a double bond position is suppressed. The method is a method for producing omega-hydroxy fatty acid ester and a precursor compound thereof of Formula (III), in which an alcohol derivative and a carboxylic acid derivative are subjected to a metathesis reaction in the presence of a catalyst to obtain a compound of Formula (III), wherein the alcohol derivative is at least one selected from the group consisting of a compound of Formula (VI) and a compound of Formula (I), and the carboxylic acid derivative is at least one selected from the group consisting of a compound of Formula (VII) and a compound of Formula (II), wherein the case where the alcohol derivative is formed of a compound of Formula (I) and the carboxylic acid derivative is formed of a compound of Formula (II) is excluded,
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Paragraph 0099; 0104; 0106
(2016/07/27)
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- FRAGRANCES FROM THE ESTERS OF FATTY ACIDS
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The invention relates to the generation of compounds, e.g., fragrance molecules with desirable olfactory properties that can be derived from readily available fatty acids.
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Paragraph 0066; 0067
(2016/03/19)
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- Agent having neurotrophic factor-like activity
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The present invention provides a pharmaceutical agent having high safety and a neurotrophic factor-like activity, which contains, as an active ingredient, any one compound included in fatty acids each having 8 carbon atoms (C8) or having 10 carbon atoms (C10) to 12 carbon atoms (C12) or fatty acid esters thereof, such as 3,7-dimethyloctanoic acid ethyl ester, geranicacidethyl ester, and the like, eachof whichhas 8 carbonatoms (C8), decanoic acid methyl ester, trans-2-decenoic acid, trans-2-decenoic acid methyl ester, trans-2-decenoic acid ethyl ester, trans-2-decenoic acid-2-decenyl ester, trans-2-decenoic acid cyclohexyl ester, trans-2-decenoic acid isopropyl ester, trans-3-decenoic acid methyl ester, trans-9-decenoic acid methyl ester, and the like, each of which has 10 carbon atoms (C10), trans-10-undecenoic acid methyl ester, trans-10-undecenoic acid ethyl ester, and the like, each of which has 11 carbon atoms (C11), and dodecanoic acid, and the like, each of which has 12 carbon atoms (C12), or salts thereof or prodrugs thereof.
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Paragraph 0033-0034
(2016/01/25)
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- PROCESS INVOLVING CROSS METATHESIS OF OLEFINS
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A method of forming a macrocyclic musk compound comprising the steps of:- i) cross-metathesizing a first olefin and a second olefin in the presence of a homogeneous transition metal catalyst comprising an alkylidene ligand, to form a statistical mixture of a hetero-dimer intermediate of said first and second terminal olefin, and homo-dimers ii) separating the hetero-dimer from the statistical mixture of hetero-and homo- dimers iii) and cyclizing the hetero-dimer intermediate to form the macrocyclic musk compound.
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Page/Page column 46
(2015/10/05)
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- Cyclic alkyl amino carbene (caac) ruthenium complexes as remarkably active catalysts for ethenolysis
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An expanded family of ruthenium-based metathesis catalysts bearing cyclic alkyl amino carbene (CAAC) ligands was prepared. These catalysts exhibited exceptional activity in the ethenolysis of the seed-oil derivative methyl oleate. In many cases, catalyst turnover numbers (TONs) of more than 100 000 were achieved, at a catalyst loading of only 3 ppm. Remarkably, the most active catalyst system was able to achieve a TON of 340000, at a catalyst loading of only 1 ppm. This is the first time a series of metathesis catalysts has exhibited such high performance in cross-metathesis reactions employing ethylene gas, with activities sufficient to render ethenolysis applicable to the industrial-scale production of linear a-olefins (LAOs) and other terminal-olefin products.
- Marx, Vanessa M.,Sullivan, Alexandra H.,Melaimi, Mohand,Virgil, Scott C.,Keitz, Benjamin K.,Weinberger, David S.,Bertrand, Guy,Grubbs, Robert H.
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supporting information
p. 1919 - 1923
(2015/02/19)
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- Complete Stereocontrol in the Synthesis of Harmonine and Novel Analogues Facilitated by a Grubbs Z-Selective Cross-Metathesis Catalyst
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(R)-Harmonine was synthesised in 15% overall yield via a six-step sequence exploiting a Z-selective cross-metathesis reaction as its centrepiece. By this strategy, the cis-olefin present in the target could be installed exclusively. The use of an alcohol and an ester as the amine precursors was crucial for isolating the cross-metathesis product from the self-metathesis products. This method was also used to prepare two novel analogues of harmonine.
- Abel, Steven-Alan G.,Olivier, Wesley J.,Pederson, Richard L.,Bissember, Alex C.,Smith, Jason A.
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p. 1815 - 1820
(2015/12/26)
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- Identification of a Grain Beetle Macrolide Pheromone and Its Synthesis by Ring-Closing Metathesis Using a Terminal Alkyne
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A major C18-macrolide was found during analysis of the frass of the storage beetle Oryzaephilus surinamensis to be (9Z,12Z,15R)-octadeca-9,12-dien-15-olide (10, cucujolide XI). The synthesis used ring-closing alkyne metathesis as a key step. The highly active 2,4,6-trimethylbenzylidyne molybdenum complex [MesCMo{OC(CF3)2Me}3] (12) allowed the use of a terminal alkyne and afforded the product in excellent yield. Bioassays proved the activity of the R-enantiomer 10 in the aggregation of the beetle. Cucujolide XI is the first macrolide pheromone oxidized at the ω-4 position.
- H?tling, Susann,Bittner, Celine,Tamm, Matthias,D?hn, Sonja,Collatz, Jana,Steidle, Johannes L. M.,Schulz, Stefan
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supporting information
p. 5004 - 5007
(2015/11/03)
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- CROSS METATHESIS APPROACH TO C11-C13 FATTY-CHAIN AMINO ESTERS FORM OLEIC ACID DERIVATIVES
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A concise method of producing nylon 11, 12, or 13 precursors from oleic acid or an ester of oleic acid is described. The method involves cross-metathesis reactions as the key C-C bond formation step. Subsequent steps are provided to convert the metathesis product to the corresponding nylon precursors. Also provided are the products of the method.
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Paragraph 0068; 0069; 0070
(2016/05/24)
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- Comparison of reactivity in the cross metathesis of allyl acetate-derivatives with oleochemical compounds
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The metathesis of unsaturated oleochemicals is an excellent tool for generating α,ω-difunctional substrates, which are useful intermediates for polymer synthesis. This article describes the cross metathesis of allyl acetate and cis-1,4-diacetoxy-2-butene with methyl 10-undecenoate and methyl oleate, which are oleochemical key substrates. Detailed optimizations led to high conversion rates and yields of the desired products under mild reaction conditions by using a low concentration of commercially available homogeneous ruthenium catalysts.
- Behr, Arno,Toepell, Stephanie
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p. 603 - 611
(2015/03/04)
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- SILOXANE-CONTAINING HYBRID MATERIALS
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The present application discloses siloxane-containing hybrid materials. For example, the present application discloses siloxane-containing hybrid materials comprising cyclic siloxanes or polyhedral siloxanes such as polymeric siloxane-containing hybrid materials comprising cyclic siloxanes or polyhedral siloxanes, methods for preparing such siloxane-containing hybrid materials, the use of such siloxane-containing hybrid materials for coating a substrate, coatings comprising the polymeric siloxane-containing hybrid materials, composites comprising a film of the polymeric siloxane-containing material coated on a substrate and compounds which are useful in preparing the siloxane-containing hybrid materials.
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- SYNTHETIC METHOD
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The invention relates to a method of alkene metathesis. In the method, at least one monoalkene is subjected to ethenolysis in the presence of a diene. The invention also relates to the use of a diene to promote an ethenolysis reaction conducted on a monoalkene.
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Page/Page column 37
(2015/09/23)
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- Valorisation of vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate with 1-hexene
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Abstract The activity and selectivity of silica-supported Hoveyda-Grubbs (HG) complex for the cross-metathesis of methyl oleate with 1-hexene to obtain 1-decene, methyl 9-tetradecenoate, 5-tetradecene and methyl 9-decenoate were studied in a batch reactor. The HG complex loading was varied between 0.87 and 11.6 wt%. Competitive secondary reactions were the self-metathesis of methyl oleate and the self-metathesis of 1-hexene. The yield to cross-metathesis products (ηC-M) was 47% when a 1-hexene/methyl oleate reactant ratio (RC6/MO) of one was employed. The ηC-M value increased with increasing 1-hexene initial concentration, reaching 87% for RC6/MO = 7. The selectivity to terminal olefins also increased at the expense of internal olefins among the cross-metathesis products when the concentration of 1-hexene was increased.
- Zelin,Nieres,Trasarti,Apesteguía
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p. 410 - 417
(2015/07/28)
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- Ionic-tagged catalytic systems applied to the ethenolysis of methyl oleate
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A novel high selective ionophilic Hoveyda-type complex for the methyl oleate ethenolysis was prepared from Grubbs first generation catalyst. Ethenolysis under classical biphasic systems in ionic liquids showed to be mass-transference limited. This drawback was successfully solved by the catalyst dispersion on high specific surface area inorganic supports through a thin layer of ionic liquids (ILs). The supported ionic liquid phase (SILP) catalyst properties were patterned by the support type, IL cation and support/IL mass ratio. The SILP prepared with the IL 1-isopentyl-3-methylimidazole hexafluorophosphate and silica showed a turnover number higher (up to 2350) than that of biphasic systems (up to 1045).
- Aydos, Guilherme L.P.,Leal, Bárbara C.,Perez-Lopez, Oscar W.,Dupont, Jairton
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- Selective ethenolysis and oestrogenicity of compounds from cashew nut shell liquid
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The ethenolysis of cardanol (2), a waste product from cashew kernel production, was carried out using a variety of metathesis catalysts. Surprisingly, the best activities and selectivities could be observed with ruthenium based 1st generation type catalysts converting cardanol (2) almost completely to the corresponding 1-octene (6) and 3-non-8-enylphenol (4), a potential detergent precursor. Detailed investigation of the reaction system showed that the high activity and selectivity were due to a combination of ethenolysis and internal self-metathesis of the unsaturated cardanol mixture, 2. Self-metathesis of cardanol (2) containing three double bonds led to the formation of 3-non-8-enylphenol (4) and 1,4-cyclohexadiene (7). The latter was crucial for a high selectivity and activity in the ethenolysis, not only of cardanol (2), but also of other substrates like methyl oleate (10) when using ruthenium based 1st generation catalysts. The endocrine disrupting properties of 3-nonylphenol and related compounds are compared. the Partner Organisations 2014.
- Julis, Jennifer,Bartlett, Stuart A.,Baader, Sabrina,Beresford, Nicola,Routledge, Edwin J.,Cazin, Catherine S.J.,Cole-Hamilton, David J.
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supporting information
p. 2846 - 2856
(2014/05/06)
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- METHOD FOR SYNTHESIZING AN OMEGA-AMINO ACID OR ESTER FROM A MONOUNSATURATED FATTY ACID OR ESTER
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A method for synthesizing ω-amino-alkanoic acids or the esters thereof from natural unsaturated fatty acids passing through an intermediate ω-unsaturated nitrile compound. The method is simple to implement and, relative to known methods, avoids the environmental constraints and economic disadvantages resulting from the reaction by-products. The method includes synthesizing an ω-amino acid (ester) of formula R3OOC—(CH2)q—CH2NH2, in which R3 is H or an n-butyl radical and q is an integral index of between 2 and 13, from a monounsaturated fatty acid (ester) of formula (R1-CH═CH—(CH2)p-COO) xR2, in which x represents 1, 2 or 3, R1 is H or a hydrocarbon radical comprising from 4 to 11 carbon atoms and, where appropriate, a hydroxyl function, R2 is H or an alkyl radical comprising from 2 to 4 carbon atoms, and may contain one or more heteroatoms, and p is an integral index of between 2 and 11, including a reaction step of ammoniation.
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Paragraph 0083
(2014/07/08)
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- Cross-metathesis approach to produce precursors of nylon 12 and nylon 13 from microalgae
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A two-step synthesis for producing methyl 12-aminododecanoate and 13-aminotridecanoate, the precursors of nylon 12 and nylon 13, from methyl oleate is described. First, methyl 11-cyano-9-undecenoate or 12-cyano-9-dodecenoate were prepared by cross metathesis of methyl oleate with either allyl cyanide or homoallyl cyanide, respectively. Subsequently, all the unsaturation of the two intermediates was hydrogenated to deliver the final products. This method represents the first synthesis of nylon 12 and 13 precursors from methyl oleate, an ester of an abundant and renewable natural fatty acid present in vegetable oil or microalgae. It also represents the shortest synthesis of nylon precursors from fatty acids, and as demonstrated in this study, can be directly applied to crude fatty acid methyl ester extracts from microalgae.
- Ameh Abel, Godwin,Oliver Nguyen, Kim,Viamajala, Sridhar,Varanasi, Sasidhar,Yamamoto, Kana
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p. 55622 - 55628
(2015/02/02)
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- Cyclic Alkyl Amino Carbene (CAAC) Ruthenium Complexes as Improved Catalysts for Ethenolysis Reactions
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Described herein are compounds and methods of catalyzing ethenolysis reactions, optionally on an industrial scale. In certain embodiments, the catalysts bear cyclic alkyl amino carbene (CAAC) ligands with an ortho substituent, such as a methyl substituent, on an N-aryl ring. When used to catalyze ethenolysis reactions, certain such compounds produce a turnover number greater than 50,000.
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Page/Page column 13
(2014/10/29)
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- General approach to prostanes B1 by intermolecular pauson-khand reaction: Syntheses of methyl esters of prostaglandin B1 and phytoprostanes 16-B1-PhytoP and 9-L1-PhytoP
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A synthetic approach to the methyl esters of Prostaglandin B1 and Phytoprostanes 16-B1-PhytoP (PPB1-I) and 9-L 1-PhytoP (PPB1-II) based on the modified Julia olefination of a formylcyclopentenone and an appropriately protected hydroxy sulfone has been developed. The cyclopentenones were efficiently prepared by intermolecular Pauson-Khand reaction of a (silyloxymethyl)alkyne. The sulfone counterpart was prepared by regioselective ring-opening of the appropriate chiral epoxides by 2-mercaptobenzothiazole. The protecting group for the alcohol functionality on the sulfone proved to be crucial. Protection as a tert-butyl ether was the best solution, giving better results than a tert-butyldimethylsilyl ether. A synthetic approach to prostanes B1 based on Julia olefination of a formylcyclopentenone and an appropriately protected hydroxy sulfone has been developed. Cyclopentenones were prepared by intermolecular Pauson-Khand reaction. Protection of the alcohol functionality of the hydroxy sulfone as a tert-butyl ether proved to be crucial. Copyright
- Vazquez-Romero, Ana,Verdaguer, Xavier,Riera, Antoni
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supporting information
p. 1716 - 1725
(2013/04/10)
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- Ruthenium-catalyzed olefin metathesis accelerated by the steric effect of the backbone substituent in cyclic (alkyl)(amino) carbenes
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Three ruthenium complexes bearing backbone-monosubstituted CAACs were prepared and displayed dramatic improvement in catalytic efficiency not only in RCM reaction but also in the ethenolysis of methyl oleate, compared to those bearing backbone-disubstitut
- Zhang, Jun,Song, Shangfei,Wang, Xiao,Jiao, Jiajun,Shi, Min
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p. 9491 - 9493
(2013/10/01)
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- Z -selective ethenolysis with a ruthenium metathesis catalyst: Experiment and theory
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The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.
- Miyazaki, Hiroshi,Herbert, Myles B.,Liu, Peng,Dong, Xiaofei,Xu, Xiufang,Keitz, Benjamin K.,Ung, Thay,Mkrtumyan, Garik,Houk,Grubbs, Robert H.
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supporting information
p. 5848 - 5858
(2013/05/22)
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- Enzyme-substrate complementarity governs access to a cationic reaction manifold in the P450BM3-catalysed oxidation of cyclopropyl fatty acids
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The products of cytochrome P450BM3-catalysed oxidation of cyclopropyl-containing dodecanoic acids are consistent with the presence of a cationic reaction intermediate, which results in efficient dehydrogenation of the rearranged probes by the enzyme. These results highlight the importance of enzyme-substrate complementarity, with a cationic intermediate occurring only when the probes used begin to diverge from ideal substrates for this enzyme. This also aids in reconciling literature reports supporting the presence of cationic intermediates with certain cytochrome P450 enzyme/substrate pairs.
- Cryle, Max J.,Hayes, Patricia Y.,De Voss, James J.
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p. 15994 - 15999
(2013/02/21)
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- ESTERAMINES AND DERIVATIVES FROM NATURAL OIL METATHESIS
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Esteramine compositions and their derivatives are disclosed. The esteramines comprise a reaction product of a metathesis-derived C10-C17 monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives with a tertiary alkanolamine. Derivatives made by quaternizing, sulfonating, alkoxylating, sulfating, and/or sulfitating the esteramines are also disclosed. In one aspect, the ester derivative of the C10-C17 monounsaturated acid or octadecene-1,18-dioic acid is a lower alkyl ester. In other aspects, the ester derivative is a modified triglyceride made by self-metathesis of a natural oil or an unsaturated triglyceride made by cross-metathesis of a natural oil with an olefin. The esteramines and derivatives are valuable for a wide variety of end uses, including cleaners, fabric treatment, hair conditioning, personal care (liquid cleansing products, conditioning bars, oral care products), antimicrobial compositions, agricultural uses, and oil field applications.
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Page/Page column 18-19
(2012/05/20)
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- Ruthenium-alkylidene catalysed cross-metathesis of fatty acid derivatives with acrylonitrile and methyl acrylate: A key step toward long-chain bifunctional and amino acid compounds
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The ruthenium catalysed cross-metathesis of fatty-esters arising from plant oils with acrylonitrile is presented. The resulting linear nitrile ester products have potential as new intermediates for polyamides synthesis. A series of commercially available catalysts are able to promote the transformation of methyl 10-undecenoate 1, dimethyl octadec-9-en-1,18-dioate 5 and methyl ricinoleate 9 with acrylonitrile and a protocol based on the slow addition of catalyst allowed TONs as high as 1900 (92% yield) to be reached for cross-metathesis with acrylonitrile. These cross-metathesis conditions have been applied to methyl acrylate and TONs up to 7600 were obtained.
- Miao,Malacea,Fischmeister,Bruneau,Dixneuf
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supporting information; experimental part
p. 2911 - 2919
(2011/12/05)
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- Highly selective ruthenium metathesis catalysts for ethenolysis
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N-Aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium metathesis catalysts are highly selective toward the ethenolysis of methyl oleate, giving selectivity as high as 95% for the kinetic ethenolysis products over the thermodynamic self-metathesis products. The examples described herein represent some of the most selective NHC-based ruthenium catalysts for ethenolysis reactions to date. Furthermore, many of these catalysts show unusual preference and stability toward propagation as a methylidene species and provide good yields and turnover numbers at relatively low catalyst loading (500 ppm). A catalyst comparison showed that ruthenium complexes bearing sterically hindered NHC substituents afforded greater selectivity and stability and exhibited longer catalyst lifetime during reactions. Comparative analysis of the catalyst preference for kinetic versus thermodynamic product formation was achieved via evaluation of their steady-state conversion in the cross-metathesis reaction of terminal olefins. These results coincided with the observed ethenolysis selectivities, in which the more selective catalysts reach a steady state characterized by lower conversion to cross-metathesis products compared to less selective catalysts, which show higher conversion to cross-metathesis products.
- Thomas, Renee M.,Keitz, Benjamin K.,Champagne, Timothy M.,Grubbs, Robert H.
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experimental part
p. 7490 - 7496
(2011/06/27)
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- METHOD FOR SYNTHESISING 9-AMINONONANOIC ACID OR THE ESTERS THEREOF FROM NATURAL UNSATURATED FATTY ACIDS
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The invention relates to a method for synthesizing 9-aminononanoic acid or the esters thereof from natural unsaturated fatty acids, comprising at least one step of metathesis of the natural fatty acid and an oxidation step by oxidative cleaving. Said synthetic method uses widely available renewable starting materials and hence economical.
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- Low pressure ethenolysis of renewable methyl oleate in a microchemical system
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Chemical equations presented. A microchemical system for ethenolysis of renewable methyl oleate was developed, in which the dual-phase, microfluidic design enabled efficient diffusion of ethylene gas into liquid methyl oleate through an increased contact area. The increased mass transfer of ethylene favored the formation of desired commodity chemicals with significantly suppressed homometathesis when compared to the bulk system. In addition to higher selectivity and conversion, this system also provides the typical advantages of a microchemical system, including the possibility of convenient scale-up.
- Park, Chan Pil,Van Wingerden, Matthew M.,Han, So-Yeop,Kim, Dong-Pyo,Grubbs, Robert H.
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experimental part
p. 2398 - 2401
(2011/06/22)
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- CATALYSTS AND PROCESSES FOR THE FORMATION OF TERMINAL OLEFINS BY ETHENOLYSIS
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The present invention relates generally to catalysts and processes for the formation of terminal olefin(s) from internal olefin(s) via ethenolysis reactions. The ethenolysis reactions may proceed with high conversion, high turnover, and/or high selectivity.
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Page/Page column 12
(2011/02/18)
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