- Photo-induced radical borylation of hemiacetals via C–C bond cleavage
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In this study, we reported a photo-induced radical borylation of hemiacetal derivatives via C–C bond cleavage. This transformation can be realized under mild conditions with simple reaction settings and irradiation of visible light. A series of substrates, including both cyclic and linear hemiacetal derivatives, were effectively transformed to the borylation product in moderate to good yields. Finally, the mechanism was studied in detail by DFT calculations, suggesting insight of the radical borylation process.
- Liu, Qianyi,Zhang, Jianning,Zhang, Lei,Mo, Fanyang
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supporting information
(2021/01/05)
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- Synthesis process of natural delta-decalactone
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The invention relates to a synthesis process of natural delta-decalactone, and belongs to the technical field of food additives, and the natural delta-decalactone is obtained by taking furfural and n-amyl alcohol as raw materials through chlorination, Grignard coupling, Piancatelli rearrangement, hydrogenation and oxidation. The purity of the delta-decalactone prepared in the synthesis process of the natural delta-decalactone can reach 98% or above, the natural degree detected by isotope mass spectrometry C14 is 95% or above, and the problems that the synthesis route of the delta-decalactone is complex and the yield is low are solved; and the experimental method is simple, convenient and feasible, the reaction condition is mild, the experimental condition is easy to realize and control, and the method has the characteristics that the raw materials are easy to obtain and rich in source, the yield is relatively high, the used catalyst can be repeatedly used and the like.
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- An effective cis-β-octahedral Mn(iii) SALPN catalyst for the Mukaiyama-Isayama hydration of α,β-unsaturated esters
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Two cis-β-MnIIISALPN catalysts were synthesised and tested in the Mukaiyama-Isayama hydration of α,β-unsaturated esters. The MnIIIEtOSALPN(acac) complex 7 is the most active and catalyses hydration with little or no detectable undesired alkene reduction. This catalyst is superior for alkene hydration compared to the originally reported Mn(dpm)3 catalyst.
- Donnelly, Paul S.,North, Andrea J.,Radjah, Natalia Caren,Ricca, Michael,Robertson, Angus,White, Jonathan M.,Rizzacasa, Mark A.
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supporting information
p. 7699 - 7702
(2019/07/09)
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- Regio- and Enantio-selective Chemo-enzymatic C?H-Lactonization of Decanoic Acid to (S)-δ-Decalactone
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The conversion of saturated fatty acids to high value chiral hydroxy-acids and lactones poses a number of synthetic challenges: the activation of unreactive C?H bonds and the need for regio- and stereoselectivity. Here the first example of a wild-type cytochrome P450 monooxygenase (CYP116B46 from Tepidiphilus thermophilus) capable of enantio- and regioselective C5 hydroxylation of decanoic acid 1 to (S)-5-hydroxydecanoic acid 2 is reported. Subsequent lactonization yields (S)-δ-decalactone 3, a high value fragrance compound, with greater than 90 % ee. Docking studies provide a rationale for the high regio- and enantioselectivity of the reaction.
- Manning, Jack,Tavanti, Michele,Porter, Joanne L.,Kress, Nico,De Visser, Sam P.,Turner, Nicholas J.,Flitsch, Sabine L.
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supporting information
p. 5668 - 5671
(2019/03/29)
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- ATP3 and MTP3: Easily Prepared Stable Perruthenate Salts for Oxidation Applications in Synthesis
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The Ley–Griffith tetra-n-propylammonium perruthenate (TPAP) catalyst has been widely deployed by the synthesis community, mainly for the oxidation of alcohols to aldehydes and ketones, but also for a variety of other synthetic transformations (e.g. diol cleavage, isomerizations, imine formation and heterocyclic synthesis). Such popularity has been forged on broad reaction scope, functional group tolerance, mild conditions, and commercial catalyst supply. However, the mild instability of TPAP creates preparation, storage, and reaction reproducibility issues, due to unpreventable slow decomposition. In search of attributes conducive to catalyst longevity an extensive range of novel perruthenate salts were prepared. Subsequent evaluation unearthed a set of readily synthesized, bench stable, phosphonium perruthenates (ATP3 and MTP3) that mirror the reactivity of TPAP, but avoid storage decomposition issues.
- Moore, Peter W.,Read, Christopher D. G.,Bernhardt, Paul V.,Williams, Craig M.
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supporting information
p. 4556 - 4561
(2018/03/13)
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- Synthetic method of high-purity delta-decalactone
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The invention provides a synthetic method of high-purity delta-decalactone. The method comprises following steps: 1-octen-3-one and dimethyl malonate are taken as raw materials, an alkaline substanceA is taken as a catalyst, the raw materials and the catalyst are subjected to micheal addition, distilled water is dropwise added to an obtained addition product, decarboxylic reaction is performed, and an intermediate product methyl-ketone-5-decenoate is obtained with content higher than 92%; methyl-5-decenoate is put in a four-port glass reactor, a sodium hydroxide solution is dropwise added, then a potassium borohydride aqueous solution is dropwise added for reduction reaction, PH value is regulated to 4-5 by hydrochloric acid after the reduction reaction is finished, stirring is stopped, and an oil layer and a water layer are obtained after stand layering; the water layer is layered again after being repeatedly extracted by MTBE, an oil phase product mixed with the MTBE is obtained andcombined with the oil layer obtained in the step three, the solvent MTBE is recovered, reduced-pressure distillation is performed, and the product delta-decalactone is obtained. According to the method, not only is content increased by 1%, but also product taste is greatly improved, and content of delta-decalactone is higher than 99%.
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Paragraph 0031; 0034-0035
(2019/01/13)
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- Biotransformation of linoleic acid into hydroxy fatty acids and carboxylic acids using a linoleate double bond hydratase as key enzyme
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Hydroxy fatty acids are used as starting materials for the production of secondary metabolites and signalling molecules as well as in the manufacture of industrial fine chemicals. However, these compounds are usually difficult to produce from renewable biomass by chemical means. In this study, linoleate double bond hydratases of Lactobacillus acidophilus NBRC 13951 were cloned for the first time. These enzymes were highly specific for the hydration of the C-9 or the C-12 double bond of unsaturated fatty acids (e.g., linoleic acid). Thereby, the enzymes allowed the selective production of hydroxy fatty acids such as 13-hydroxy- cis -9-octadecenoic acid and 10-hydroxy- cis -12-octadecenoic acid from linoleic acid. In addition, the hydroxy fatty acids were further converted into industrially relevant carboxylic acids (e.g., 12-hydroxy-cis-9-dodecenoic acid, a, w-tridec-9-enedioic acid) and lactones (i.e., d-decalactone, g-dodecelactone) via whole-cell biocatalysis using an enzyme cascade. This study thus contributes to the preparation of hydroxy fatty acids, unsaturated carboxylic acids, and lactones from renewable unsaturated fatty acids.
- Oh, Hye-Jin,Kim, Sae-Um,Song, Ji-Won,Lee, Jung-Hoo,Kang, Woo-Ri,Jo, Ye-Seul,Kim, Kyoung-Rok,Bornscheuer, Uwe T.,Oh, Deok-Kun,Park, Jin-Byung
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p. 408 - 416
(2015/03/05)
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- Synthesis of d-decalactone
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The application and shortcomings of typical synthetic method of title d-decalactone was introduced in brief. A synthesis of 2-pentylidene cyclopentanone starting from cyclopentanone and n-valeraldehyde through aldol condensation, followed by dehydration, was studied and the yield reached 86.3 %. Then 2-pentenyl cyclopentanone was prepared in a yield of 91.5 % from 2-pentylidene cyclopentanone with a hydrogenation methodology under atmospheric pressure and use Pt/C as catalytic. Through Baeyer-Villiger oxidation, d-decalactone was synthesized in a yield of 61.2 %. Experiments by orthogonal experiment method to optimize the reaction conditions to determine the response of a reasonable process parameters and the analysis of the factors affecting the reactions. The structures and compositions of these compounds were accomplished by IR and GC-MS.
- Bu, Jia,Li, Guangxue,Zhao, Mingzhu,Li, Jiaming,Jiang, Feng,Zhan, Hualu,Chu, Yang
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p. 4520 - 4522
(2013/07/19)
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- Screening of a selection of commercially available homogeneous Ru-catalysts in valuable olefin metathesis transformations
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A library of thirteen different commercially available Ru-based catalysts was evaluated in valuable metathesis reactions for the production of fragrance and bioactive molecule precursors. Rigorous library screening clearly illustrated the different catalytic behaviour of the catalyst selection and highlighted its significant advantage to provide efficiency in specific metathesis applications. Interestingly, this strategy offered substantial improvement over the state of the art, with the efficient synthesis of the macrocyclic Exaltolide 2 at low catalyst loading and dilution conditions. The Royal Society of Chemistry 2013.
- Caijo, Frederic,Tripoteau, Fabien,Bellec, Aurelien,Crevisy, Christophe,Basle, Olivier,Mauduit, Marc,Briel, Oliver
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p. 429 - 435
(2013/03/14)
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- Oxidation of the cyclopentanone and cyclohexanone alkyl derivatives in a pseudohomogeneous system without a phase transfer agent
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The reaction of catalytic oxidation of C5-C12 alkyl- and cycloalkylcyclopentanones and -cyclohexanones to lactones in a pseudohomogeneous system without the participation of phase transfer agents was investigated. It was established that the catalytic systems prepared on the basis of molybdenum and tungsten blue (MeOnBrm, where Me = Mo, W, n = 1, 2, m = 2, 3) and H3PO4 deposited on powdered activated carbon AG-3 at 40-60°C, at 5-6 h duration exhibit a high selectivity in the reaction of nucleophilic addition of oxygen to the ketones with the formation of the valero- and caprolactones. Pleiades Publishing, Ltd., 2011.
- Alimardanov,Garibov,Abbasov,Sadygov,Abdullaeva,Dzhafarova
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experimental part
p. 1664 - 1670
(2011/12/02)
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- Nanoflow microreactor for dramatic increase not only in reactivity but also in selectivity: Baeyer-Villiger oxidation by aqueous hydrogen peroxide using lowest concentration of a fluorous lanthanide catalyst
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Not only the reaction rate but also the regioselectivity in the scandium bis(perfluorooctanesulfonyl)amide-catalyzed Baeyer-Villiger reaction is remarkably increased by the development of the fluorous nanoflow microreactor system continuously controlled by the nanofeeder DiNaS (Direct Nanoflow System) even in the lowest concentration of the catalyst (?0.1 mol%). The Baeyer-Villiger reaction completes within few seconds as a contact time in the nanoflow microreactor to give the lactone products with high regioselectivity without hydrolysis.
- Mikami, Koichi,Yamanaka, Masahiro,Islam, Md. Nazrul,Tonoi, Takayuki,Itoh, Yoshimitsu,Shinoda, Masaki,Kudo, Kenichi
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p. 592 - 596
(2008/03/27)
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- Lewis acid-catalysed isomerisation of thionolactones to thiolactones: inversion of configuration
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Boron trifluoride and indium(III) trifluoromethanesulfonate were found to efficiently catalyse the isomerisation of thionolactones to thiolactones in good yields. When applied to an optically active γ-thionolactone, the isomerisation reaction proceeded with a complete inversion of configuration by using BF3·Et2O.
- Filippi, Jean-Jacques,Fernandez, Xavier,Du?ach, Elisabet
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p. 6067 - 6070
(2007/10/03)
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- PROCESS
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The present invention relates to a process for preparing a lactone. The process comprises the steps of reacting an aldehyde with an organic halide in a carbon chain extension reaction to form an alcohol compound comprising a functional group capable of allowing for carbonylation of said alcohol compound, and then reacting said alcohol compound in a carbonylation reaction to form an hydroxycarboxylic acid; and cyclising the hydroxycarboxylic acid to produce the lactone.
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Page/Page column 21
(2010/11/08)
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- IBX/n-Bu4NBr/CH2Cl2-H2O: A new mild system for selective oxidation of secondary alcohols
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A new alternative system for the chemoselective oxidation of secondary hydroxyl group to ketone with IBX/n-Bu4NBr in CH2Cl 2-H2O has been developed. Under the reaction conditions, the secondary hydroxyl group was highly chemoselectively oxidized to the corresponding ketone, in moderate to good yields at rt, in the presence of primary hydroxyl group within the same molecule.
- Kuhakarn, Chutima,Kittigowittana, Krisada,Pohmakotr, Manat,Reutrakul, Vichai
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p. 8995 - 9000
(2007/10/03)
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- Cycloisomerization of olefinic carboxylic acids catalyzed by trifluoromethanesulfonic acid
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The trifluoromethanesulfonic acid-catalyzed cyclization of various differently substituted unsaturated carboxylic acids affords selectively substituted lactones in good yields. The reactions use 0.5 to 5% molar ratio of catalyst and can be run without solvent.
- Coulombel, Lydie,Dunach, Elisabet
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p. 153 - 160
(2007/10/03)
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- Nanoflow system for perfect regiocontrol in the Baeyer-Villiger oxidation by aqueous hydrogen peroxide using lowest concentration of a fluorous lanthanide catalyst
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The scandium bis(perfluorooctanesulfonyl)amide-catalyzed Baeyer-Villiger reaction significantly increased the regioselectivity as well as the reaction rate by nanoflow system continuously controlled by a nanofeeder even in the lowest concentration of the catalyst (0.1mol%). The Baeyer-Villiger reaction completed within few seconds as a contact time in the microcell to afford the lactone products high regioselectively without hydrolysis.
- Mikami, Koichi,Islam, Md. Nazrul,Yamanaka, Masahiro,Itoh, Yoshimitsu,Shinoda, Masaki,Kudo, Kenichi
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p. 3681 - 3683
(2007/10/03)
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- A new environmentally benign catalytic process for the asymmetric synthesis of lactones: Synthesis of the flavouring δ-decalactone molecule
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The system Sn-Beta/hydrogen peroxide is applied to the Baeyer-Villiger oxidation of delfone to δ-decalactone, which is an industrial fragrance. The reaction is carried out without solvent and with a substrate/catalyst ratio > 200 (wt/wt). Starting with an enantiomerically enriched delfone it is shown that the rearrangement occurs with retention of configuration at the migrating asymmetric carbon atom, and enantiomerically enriched δ-decalactone is obtained as product. This process offers clear advantages over the actual industrial production that uses peracids as oxidants.
- Corma, Avelino,Iborra, Sara,Mifsud, Mari?a,Renz, Michael,Susarte, Manuel
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p. 257 - 262
(2007/10/03)
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- PROCESS FOR THE PREPARATION OF LACTONES OR EPOXIDES
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The present invention relates to a process for the oxidation, in an inert solvent, of a non-aromatic or non-enonic ethylenic bond or of a non-conjugated cyclic ketones into the corresponding epoxides, respectively lactone, using H?2#191O?2#191 as oxidant, a content in water of the reaction medium below 15% w/w and, as sole catalyst, an alkaline or alkaline earth salt or complex.
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- Compounds having protected hydroxy groups
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The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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- Compounds having protected hydroxy groups
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The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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- Precursor compounds
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The compounds of the formula I are precursors for organoleptic and antimicrobial compounds. The latter are generated in the presence of skin bacteria, enzymes or acidic or alkaline conditions. One precursor molecule can provide one or more different compounds.
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- Beta-ketoester compounds
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The beta-ketoesters of formula I are useful as precursors for organoleptic compounds, especially for flavors, fragrances and masking agents and antimicrobial compounds.
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- New strategies in carbonylation chemistry: The synthesis of δ-lactones from saturated alcohols and CO
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This paper describes the δ-carbonylation of saturated alcohols which uses a 1,5-hydrogen-transfer reaction of alkoxyl radicals and subsequent carbonylation at the δ-carbon atoms as the key. The carbonylation reactions of five classes of saturated alcohols, namely, primary alcohols having primary δ-carbons, primary alcohols having secondary δ-carbons, primary alcohols having tertiary δ-carbons, secondary alcohols having primary δ- carbons, secondary alcohols having secondary δ-carbons, were carded out, in which lead tetraacetate (LTA) was used as a one-electron oxidant to generate the alkoxyl radicals. Carbonylation of these saturated alcohols, except for primary alcohols having tertiary δ-carbons, took place to afford δ-lactones in moderate to good yields. The mechanism of the remote carbonylation likely involves (1) alkoxyl radical generation via LTA oxidation of a saturated alcohol, (2) conversion of this alkoxyl radical to a δ-hydroxyalkyl radical by a 1,5-hydrogen-transfer reaction, (3) CO trapping of the δ-hydroxyalkyl radical yielding an acyl radical, and (4) oxidation and cyclization of the acyl radical to give a δ-lactone. A metal salt-free system was also tested for a substrate derived from a tertiary alcohol having a secondary δ- carbon; the photolysis of an alkyl 4-nitrobenzenesulfenate under CO pressures gave a δ-lactone in moderate yield.
- Tsunoi, Shinji,Ryu, Ilhyong,Okuda, Tohru,Tanaka, Minoru,Komatsu, Mitsuo,Sonoda, Noboru
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p. 8692 - 8701
(2007/10/03)
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- Catalytic oxidation of alkyl- and cycloalkylcyclanones into lactones
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Pilot-plant syntheses of alkyl and cycloalkylcyclanones and their subsequent liquid-phase oxidation into lactones are described. Characteristics of resulting intermediates and target products are reported.
- Abbasov,Alimardanov,Suleimanova
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p. 621 - 626
(2007/10/03)
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- DIRECT SYNTHESIS OF δ-LACTONES FROM 2-(3-LITHIOPROPYL)-1,3-DIOXOLANE AND CARBONYL COMPOUNDS
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The reaction of 2-(3-lithiopropyl)-1,3-dioxolane (2), prepared in situ by lithiation of the chloroacetal 1 with lithium naphthalenide at -78 deg C, with aldehydes and ketones followed by hydrolysis with hydrochloric acid and final oxidation with PCC or Jones reagent yields the corresponding δ-lactones 5.
- Ramon, Diego J.,Yus, Miguel
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p. 3767 - 3770
(2007/10/02)
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- A Selective and Efficient Method for Alcohol Oxidations Mediated by N-Oxoammonium Salts in Combination with Sodium Bromite
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The oxidation of primary and secondary alcohols leading to aldehydes, carboxylic acids, and ketones has been carried out in a N-oxoammonium salts-NaBrO2 system.Sodium bromite as a stoichiometric oxidizing reagent activates N-oxyl compounds (recycling catalysts) to their N-oxoammonium salts in a weakly basic medium, which oxidize primary hydroxyl groups preferentially rather than secondary ones to the corresponding aldehydes.Calcium hypochlorite is used as an alternative terminal oxidant in the same media.The procedure, applicable to the selective formation of γ- and δ-lactones, β-hydroxy aldehydes, and 2-acetoxy ketones, is advantageous in terms of reagent cost, safety, and ease of operation.
- Inokuchi, Tsutomo,Matsumoto, Sigeaki,Nishiyama, Tokio,Torii, Sigeru
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p. 462 - 466
(2007/10/02)
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- Process for the production of isosolanone and solanone, intermediates useful in said process and organoleptic uses of said intermediates
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Described is a novel genus of compounds defined according to the structure: STR1 wherein Z represents hydrogen, MgX and the moiety having the structure: STR2 and X represents chlor, bromo, or iodo; as well as 5-isopropyl-8-methyl-5,8-nonadien-2-one; uses of same as intermediates in a process for producing isosolanone and solanone; and organoleptic uses of 5-isopropyl-8-methyl-5,8-nonadien-2-one and 2,6-dimethyl-5-methylene-1-hepten-4-ol. The novel process of our invention involved the steps of: (i) formation of the compound having the structure: STR3 by means of reacting 3-methyl-2-methylenebutanal with the compound having the structure: STR4 (ii) acid hydrolysis of the resulting compound in order to form 2,6-dimethyl-5-methylene-1-heptene-4-ol; (iii) reaction of 2,6-dimethyl-5-methylene-1-hepten-4-ol with methyl aceto acetate in order to form 2,6-dimethyl-5-methylene-1-hepten-4-yl aceto acetate or, directly, 5-isopropyl-8-methyl-5,8-nonadiene-2-one; (iv) reacting 2,6-dimethyl-5-methylene-1-hepten-4-yl aceto acetate in the presence of an appropriate catalyst to form the 5-isopropyl-8-methyl-5,8-nonadiene-2-one; and (v) isomerizing the 5-isopropyl-8-methyl-5,8-nonadien-2-one in order to form a mixture of solanone and the isosolanone or 5-isopropyl-8-methyl-5,8-nonadiene-2-one.
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- Indirect Electrooxidation of Alkohols and Aldehydes by Using a Double Mediatory System Consisting of RuO4/RuO2 and Cl+/Cl- Redoxes in an Aqueous-Organic Two-Phase System
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A double mediatory system consisting of RuO4/RuO2 and Cl+/Cl- redox couples has been developed for the indirect electrooxidation of alcohols and aldehydes.The reaction proceeds in the following manner: (1) oxidation of the substrate with ruthenium tetraoxide (RuO4) in the organic layer, (2) regeneration of ruthenium tetraoxide from ruthenium dioxide (RuO2) with active chlorine species (Cl2 or +), and (3) oxidation of chloride ion to + on the anode in the aqueous layer.The range of applicability of the present procedure is discussed by oxidations of (1)secondary alcohols to ketones, (2) primary alcohols and aldehydes to carboxylic acid, (3) 1,n-diols to lactones and keto acids, and (4) carbohydrate derivatives.
- Torii, Sigeru,Inokuchi, Tsutomu,Sugiura, Toyoyuki
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p. 155 - 161
(2007/10/02)
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- A NEW SYNTHESIS OF α,β-UNSATURATED γ- AND δ-LACTONS VIA INTRAMOLECULAR ACYLATION OF α-SULFINYL CARBANION
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A new synthesis of α,β-unsaturated γ- and δ-lactones involving the intramolecular acylation of α-sulfinyl carbanion followed by pyrolisis is described.
- Pohmakotr, Manat,Jarupan, Prapanpong
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p. 2253 - 2256
(2007/10/02)
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- Synthesis of γ- and δ-Lactones via Radical CC-Bond Formation Reaction
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Lactones 5 and 6 can be synthesized via solvomercuration of alkenes 1 and reductive CC-bond formation with acrylonitrile.
- Giese, Bernd,Hasskerl, Thomas,Luening, Ulrich
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p. 859 - 861
(2007/10/02)
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- A VERY SIMPLE SYTHESIS OF NATURAL SATURATED δ-SUBSTITUTED δ-LACTONES. THE PHEROMONE OF Vespa orientalis
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Very facile syntheses of racemic massoia lacton and the pheromone of Veapa orientialis have been achieved starting from dehydroacetic acid.
- Bacardit, Ramon,Moreno-Manas, Marcial
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