- INSECT PHEROMONES AND THEIR ANALOGUES XL. SYNTHESIS OF DODEC-3Z-EN-11RS-OLIDE (FERRULACTONE II - A RACEMIC ANALOGUE OF A COMPONENT OF THE AGGREGATION PHEROMONE OF Cryptolestes ferrugineus
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A new route, based on the partial ozonolysis of ω-acetyl derivatives of alk-1-en-4-ynes, is proposed for the synthesis of 11RS-hydroxydodec-3Z-enoic acid, the cyclization of which gives dodec-3Z-en-11RS-olide (ferrulactone II) - a racemic analogue of one of the macrolide components of the aggregation pheromone of the rust-red grain beetle.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Botsman, L. P.,Vakhidov, R. R.,Ladenkova, I. M.,et al.
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- Two approaches to the synthesis of 9-oxo-and 10-hydroxy-2E-decenoic acids, important components of queen substance and royal jelly of honeybees Apis mellifera
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Two approaches to the synthesis of 9-oxo-and 10-hydroxy-2E-decenoic acids, biologically active components of queen substance and royal jelly of honeybees, respectively, were proposed starting with allyl bromide and 1,7-octadiene and using chemo-and regioselective transformations of the common intermediate building block 7-octen-1-ylacetate.
- Ishmuratov,Yakovleva,Tambovtsev,Legostaeva,Kravchenko,Ishmuratova,Tolstikov
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Read Online
- Catalytic removal of tert-butyldimethylsilyl (TBS) ether by PVP-I
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A mild, efficient and rapid protocol the deprotection of alcoholic TBDMS ethers using PVP-1 as catalyst in methanol, the procedure of deprotection of various TBDMS ethers were found to be very convenient, easy work-up, high yielding.
- Ke, Yanxiong,Lu, Guangying,Ren, Jiangmeng,Wang, Di,Zeng, Bu-Bing
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- Rhenium-catalyzed deoxydehydration of renewable triols derived from sugars
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An efficient method for the catalytic deoxydehydration of renewable triols, including those obtained from 5-HMF, is described. The corresponding unsaturated alcohols were obtained in good yields using simple rhenium(vii)oxide under neat conditions and ambient atmosphere at 165 °C.
- Wozniak, Bartosz,Li, Yuehui,Tin, Sergey,De Vries, Johannes G.
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supporting information
p. 4433 - 4437
(2018/10/17)
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- SYNTHESIS OF PHEROMONES AND RELATED MATERIALS VIA OLEFIN METATHESIS
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Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.
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Paragraph 0257
(2018/09/12)
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- Cycloaddition Reactions of Cobalt-Complexed Macrocyclic Alkynes: The Transannular Pauson-Khand Reaction
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The Pauson-Khand reaction is a powerful tool for the synthesis of cyclopentenones through the efficient [2 + 2 + 1] cycloaddition of dicobalt alkyne complexes with alkenes. While intermolecular and intramolecular variants are widely known, transannular versions of this reaction are unknown and the basis of this study. Macrocyclic enyne and dienyne complexes were readily synthesized by palladium(II)-catalyzed oxidative macrocyclizations of bis(vinyl boronate esters) or ring-closing metathesis reactions followed by complexation with dicobalt octacarbonyl. Several reaction modalities of these macrocyclic complexes were uncovered. In addition to the first successful transannular Pauson-Khand reactions, other intermolecular and transannular cycloaddition reactions included intermolecular Pauson-Khand reactions, transannular [4 + 2] cycloaddition reactions, intermolecular [2 + 2 + 2] cycloaddition reactions, and intermolecular [2 + 2 + 1 + 1] cycloaddition reactions. The structural and reaction requirements for each process are presented.
- Karabiyikoglu, Sedef,Boon, Byron A.,Merlic, Craig A.
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p. 7732 - 7744
(2017/08/14)
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- METHOD FOR PRODUCING 7-OCTENAL
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Provided is a method for highly selectively producing 7-octenal with a high conversion ratio through the isomerization reaction of 2,7-octadiene-1-ol. Specifically, provided is a method for producing 7-octenal, in which a copper-based catalyst is obtained by reducing a copper-based catalyst precursor described below, and an isomerization reaction of 2,7-octadiene-1-ol is caused in a gas phase using a fixed-bed reaction in the presence of the obtained copper-based catalyst. The copper-based catalyst precursor: a copper-based catalyst precursor obtained by calcining a mixture containing copper, iron, aluminum, and calcium silicate in which an atomic ratio of iron and aluminum to copper [(Fe+Al)/Cu] is in a range of 1.71 to 2.5, an atomic ratio of aluminum to iron [Al/Fe] is in a range of 0.001 to 3.3, and calcium silicate is contained in a range of 15% by mass to 65% by mass at a temperature in a range of 500°C to 1,000°C.
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Paragraph 0148; 0149; 0150; 0151
(2015/07/22)
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- Diastereoselective synthesis of the C14-C29 fragment of amphidinol 3
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An efficient stereoselective synthesis of the C14-C29 fragment highlighting a coupling reaction between a 1,3-dithiane derivative and an α-branched aldehyde was realized. This highly convergent synthesis involved two chiral pools, l-malic acid and (+)-camphorsulfonic acid, which are the starting compounds to control the six stereogenic centers present in the C14-C29 fragment of amphidinol 3.
- Rival, Nicolas,Hanquet, Gilles,Bensoussan, Charlelie,Reymond, Sebastien,Cossy, Janine,Colobert, Francoise
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p. 6829 - 6840
(2013/10/01)
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- Vapor-phase catalytic dehydration of terminal diols
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Vapor-phase catalytic reactions of several terminal diols were investigated over several rare earth oxides, such as Sc2O3, Y 2O3, CeO2, Yb2O3, and Lu2O3. Sc2O3 showed selective catalytic activity in the dehydration of terminal diols with long carbon chain, such as 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, to produce the corresponding unsaturated alcohols. In the dehydration of 1,6-hexanediol, 5-hexen-1-ol was produced with selectivity over 60 mol%, together with by-products such as ε-caprolactone and oxacycloheptane. In the dehydration of 1,10-decanediol, 9-decen-1-ol was produced with selectivity higher than 70 mol%. In addition to Sc 2O3, heavy rare earth oxides such as Lu2O 3 as well as monoclinic ZrO2 showed moderate selectivity in the dehydration of the terminal diols.
- Abe, Katsutoshi,Ohishi, Yusuke,Okada, Takuto,Yamada, Yasuhiro,Sato, Satoshi
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experimental part
p. 419 - 424
(2012/02/03)
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- Tetraols as templates for the synthesis of large endo-functionalized macrocycles
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Forty-six- and fifty-membered endo-functionalized macrocycles were obtained by template syntheses with new stiff tetracyclic tetraols 10 and 11. Reaction of dialkenylatedboronic acids 1 with template molecules 10 and 11 generated preorganized bisboronic esters 18 and 19, which were cyclized by ring-closing olefin metathesis. Resulting bimacrocycles 20 and 21 were obtained in ca. 60% yield when alkenyl chains of sufficient lengths were used. The E/E, E/Z, and Z/Z mixtures were hydrogenated to give saturated bimacrocycles 24 and 25 in excellent yields. The removal of the tetraol templates was possible by hydrolysis in the presence of dimethyl sulfate, which was needed to trap the liberated template. Thus, bis-endo-boronic acids 27e and 27f were obtained. The relative stereochemistry of the diastereoisomeric templates and the bimacrocyclic nature of the cyclization products were proven by X-ray structure analyses (for 12 and 26d).
- Stoltenberg, Dennis,Luethje, Sonja,Winkelmann, Ole,Naether, Christian,Luening, Ulrich
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experimental part
p. 5845 - 5859
(2011/12/05)
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- Self-assembly of semifluorinated dendrons attached to electron-donor groups mediates their π-stacking via a helical pyramidal column
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Semifluorinated first-generation self-assembling dendrons attached via a flexible spacer to electron-donor molecules induce π-stacking of the donors in the center of a supramolecular helical pyramidal column. These helical pyramidal columns self-organize in various columnar liquid crystal phases that mediate self-processing of large single crystal liquid crystal do mains of columns and self-repair their intracolumnar structural defects. In addition, all supramolecular columns exhibit a columnar phase at lower temperatures that maintains the helical pyramidal columnar supramolecular structure and displays higher intracolumnar order than that in the liquid crystals phases. The results described here demonstrate the universality of this concept, the power of the fluorous phase or the fluorophobic effect in self-assembly and the unexpected generality of pyramidal liquid crystals.
- Percec, Virgil,Glodde, Martin,Peterca, Mihai,Rapp, Almut,Schnell, Ingo,Spiess, Hans W.,Bera, Tushar K.,Miura, Yoshiko,Balagurusamy, Venkatachalapathy S. K.,Aqad, Emad,Heiney, Paul A.
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p. 6298 - 6314
(2008/12/23)
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- Synthesis of C3-C9-alkenyl 2,3-unsaturated glucosides from glucose and some alkenols
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C3-C9-Alkenyl 2,3-unsaturated glucosides have been synthesized from glucose and C3-C9-alkenols by using Ferrier reaction with boron trifluoride etherate (BF3·Et2O) as Lewis acid catalyst in key step.
- Konstantinovic,Predojevic,Gojkovic,Ratkovic,Dimitrijevic,Mojsilovic
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p. 802 - 805
(2007/10/03)
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- A novel hydrogen transfer hydroalumination of alkenes with triisobutylaluminum catalyzed by Pd and other late transition metal complexes
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Hydrogen transfer hydroalumination of terminal alkenes and dienes can be achieved with 1.1 equiv. of (i-Bu)3Al and catalytic amounts of Cl2Pd(PPh3)2 and other late transition metal complexes containing Co, Rh, Ni, and Pt at ambient temperature in high yields.
- Gagneur, Sebastien,Makabe, Hidefumi,Negishi, Ei-Ichi
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p. 785 - 787
(2007/10/03)
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- Method for the synthesis of bis-tetrahydrofuranyl Annonaceous acetogenins
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A method for the synthesis of bis-tetrahydrofuranyl Annonaceous acetogenins, including the natural products and analogs thereof, is provided which proceeds by the Pd-mediated coupling of a bis-tetrahydrofuranyl-subunit comprising a terminal alkyne, with a (C4)-hydroxybutenolide subunit comprising a terminal vinyl iodide, followed by selective reduction of the resulting enyne.
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- First Total Synthesis of Niphatesines A-D and Assignment of Absolute Configuration
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Regio/Enantioselective synthesis of niphatesines A-D is achieved making use of Pd(0) assisted 3-alkylation of pyridine as the key step.Absolute configuration of niphatesines C and D is established.
- Rao, A. V. Rama,Reddy, Gongiti Ravindra
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p. 8329 - 8332
(2007/10/02)
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- POLYACETYLENES FROM THE ROOTS OF PANAX GINSENG
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Key Word Index - Panax ginseng; Araliaceae; polyacetylene; ginsenoyne A; ginsenoyne B; ginsenoyne C; ginsenoyne D; ginsenoyne E. Abstract - Five new polyacetylenes named ginsenoynes A, B, C, D and E were isolated from the hexane extract of the root of Panax ginseng.These structures were determined by spectral and chemical methods.
- Hirakura, Kazuhiro,Morita, Makoto,Nakajima, Kaoru,Ikeya, Yukinobu,Mitsuhashi, Hiroshi
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p. 3327 - 3333
(2007/10/02)
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- SYNTHESIS AND BIOMETHYLENATION OF TWO HOMOALLYLICALLY FLUORINATED OLEIC ACIDS
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Methyl 7-fluorooleate and methyl 12-fluorooleate have been synthesized in racemic form.Both of these compounds are incorporated into L. plantarum but are methylenated to a different extent.
- Buist, Peter H.,Findlay, Judy M.,Leger, Gabriel,Pon, Robert A.
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p. 3891 - 3894
(2007/10/02)
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- Processes for producing 7-octen-1-al and derivatives thereof
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There are disclosed a process for producing 7-octen-1-al which comprises isomerizing 2,7-octadien-1-ol in the presence of a catalyst comprising oxides of at least two metals selected from the group consisting of copper, chromium and zinc and processes for producing derivatives of 7-octen-1-al.
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- EVOLUTION THERMIQUE DE N-OXYDES D'ω-DIALKYLAMINO ALCANOLS-1
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The thermolysis of ω-dimethylamino-1-alkanol N-oxides affords ω-hydroxy-1-alkenes with dimethylhydroxylamine in good yields.The other basic products (amino alcohol and isoxazolidine) involve oxidation-reduction process between the tertiary amine N-oxide and dimethylhydroxylamine, followed by 1,3-dipolar cycloaddition reaction.Pyrolysis of 5-piperidino-1-pentanol N-oxide proceeds on a path similar to the N-dimethyl compounds.The elimination of an hydrogen atom of the heterocycle does not occur: the preferred planar transition state cannot be attained because of thesteric requirements of the ring.
- Barbry, Didier,Hasiak, Bruno
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p. 2410 - 2414
(2007/10/02)
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- Mechanistic Studies on Non-Heme Iron Monooxygenase Catalysis: Epoxidation, Aldehyde Formation, and Demethylation by the ω-Hydroxylation System of Pseudomonas oleovorans
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In previous work we have established that the "ω-hydroxylation" system of P. oleovorans readily converts terminal olefins to the corresponding 1,2-oxides and does so stereoselectively.We also demonstrated loss of olefin configuration during enzymatic epoxidation, a result inconsistent with a concerted epoxidation mechanism (J.Am.Chem.Soc. 1977, 99, 2017-2024).Since loss of olefin configuration is unprecedented for monooxygenase-catalyzed epoxidations these studies have been confirmed with isolated enzymes and further extended in order to probe the mechanism of non-heme iron monooxygenase catalysis.Enzymatic epoxidation of both cis- and trans-1-deuterio-1-octene proceeds with about 70percent inversion of the olefinic configuration, with corresponding results being obtained for the two olefins.As we reported in a preliminary communication (Bio/Technology 1983, 1, 677-686, the ω-hydroxylation system also produces aldehydes from olefins.Aldehyde formations exhibits the reaction characteristics expected for the usual oxygenase pathway.Deuterium migration from C-1 to C-2 occurs in formation of aldehyde from olefin, although loss of deuterium also occurs.The ω-hydroxylation system was found to efficiently catalyze O-demethylation of heptyl methyl ether, the first demonstration of such activity for a non-heme iron monooxygenase of this type.Taken together, the results provide support for a two-step mechanism involving enzyme generated species with cationic and/or radical character, which accounts for the stereoselectivity, configurational loss, substrate specificity, formation of aldehydes with deuterium migration, and demethylation activity exhibited by this enzyme system.
- Katopodis, Andreas, G.,Wimalasena, Kandatege,Lee, Joseph,May, Sheldon W.
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p. 7928 - 7935
(2007/10/02)
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- REGIO- AND STEREO-SELECTIVITIES IN THE TITANIUM COMPLEX CATALYZED HYDROBORATION OF CARBON-CARBON DOUBLE BONDS IN VARIOUS UNSATURATED COMPOUNDS
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The titanium complex prepared from TiCl3 and NaBH4 in THF in the presence of 18-crown-6 promotes the catalytic hydroboration of carbon-carbon double bonds in alkenes, alkadienes and unsaturated ethers with NaBH4, giving sodium organoborates which can be converted into alcohols by oxidation with H2O2/CH3ONa.The reaction proceeds with high regio- and stereo-selectivities.
- Lee, Hyung Soo,Isagawa, Kakuzo,Toyoda, Hiromu,Otsuji, Yoshio
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p. 673 - 676
(2007/10/02)
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- ETUDE DES INTERACTIONS ENTRE FONCTIONS ALCOOL ET AMINE: EVOLUTION THERMIQUE D'HYDROXYDES ET DE SELS D'ω-TRIALKYLAMMONIO ALCANOLS-1
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The thermolysis of ω-hydroxyalkyltrialkylammonium hydroxides (Φ=4-8) was investigated: Elimination to alkenol competes with substitution to amino alcohol; the hydroxy group can be alkylated into aliphatic ethers by an intermolecular process; the intramolecular cyclization into cyclic ethers is important only when ω=4.Substitution reaction in amino alcohols is the main pathway for the thermolysis of ω-hydroxyalkyltrimethylammonium acetates (ω=5,6) and chloride (ω=6).
- Barbry, Didier,Hasiak, Bruno
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p. 1734 - 1744
(2007/10/02)
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- PHEROMONES OF INSECTS AND THEIR ANALOGS. V. A NEW APPROACH TO THE SYNTHESIS OF THE SEX PHEROMONES OF INSECTS OF THE ORDER Lepidoptera WHICH IS BASED ON THE SELECTIVE OZONOLYSIS OF 1-METHYLCYCLOOCTA-1Z,5Z-DIENE
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A new synthesis of 1-acetoxyalk-Z-enes (sex pheromones of insects of the order Lepidoptera) has been developed which is based on the selective ozonolysis of 1-methylcycloocta-1Z-5Z-diene - a cooligomer of isoprene and butadiene.
- Tolstikov, G. A.,Odinokov, V. N.,Galeeva, R. I.,Bakeeva, R. S.,Akhunova, V. R.
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p. 219 - 224
(2007/10/02)
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- Cyclobutyl substituted derivatives of prostaglandin analogs
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Novel C15 cyclobutyl analogs or derivatives of prostaglandins of the E-, A- and F-classes are useful modifiers of smooth muscle activity. The compounds have valuable pharmacological properties such as platelet antiaggregating agents, gastric antisecretory agents and brochodilating agents.
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