- METHOD FOR CONVERTING HYDROXYL GROUP OF ALCOHOL
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The present invention relates to: a method for converting a hydroxyl group of an alcohol; and a catalyst which makes the method possible. A method for converting a hydroxyl group of an alcohol according to the present invention is characterized by producing a compound represented by CH(R1)(R2)Nu (wherein R1, R2 and Nu are as defined below) by reacting an alcohol represented by CH(R1)(R2)OH (wherein each of R1 and R2 represents a hydrogen atom, an optionally substituted alkyl group, or the like) and a compound having an active proton, which is represented by H-Nu (wherein Nu represents a group represented by —CHX1-EWG1 or —NR3R4; X1 represents a hydrogen atom or the like; EWG1 represents an electron-withdrawing group; and each of R3 and R4 represents a hydrogen atom, an optionally substituted alkyl group, or the like), with each other in the presence of a complex of a group 7-11 metal of the periodic table and at least one solid base that is selected from the group consisting of layered double hydroxides, composite oxides and calcium hydroxide.
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Paragraph 0493-0494
(2021/02/19)
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- Chelation-Assisted C-H and C-C Bond Activation of Allylic Alcohols by a Rh(I) Catalyst under Microwave Irradiation
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Chelation-assisted Rh(I)-catalyzed ketone synthesis from allylic alcohols and alkenes through C-H and C-C bond activations under microwave irradiation was developed. Aldimine is formed via olefin isomerization of allyl alcohol under Rh(I) catalysis and condensation with 2-amino-3-picoline, followed by continuous C-H and C-C bond activations to produce a dialkyl ketone. The addition of piperidine accelerates the reaction rate by promoting aldimine formation under microwave conditions.
- Lee, Chang-Hee,Jun, Chul-Ho
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p. 736 - 741
(2017/11/27)
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- C -Methylation of Alcohols, Ketones, and Indoles with Methanol Using Heterogeneous Platinum Catalysts
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A versatile, selective, and recyclable heterogeneous catalytic method for the methylation of C-H bonds in alcohols, ketones, and indoles with methanol under oxidant-free conditions using a Pt-loaded carbon (Pt/C) catalyst in the presence of NaOH is reported. This catalytic system is effective for various methylation reactions: (1) the β-methylation of primary alcohols, including aryl, aliphatic, and heterocyclic alcohols, (2) the α-methylation of ketones, and (3) the selective C3-methylation of indoles. The reactions are driven by a borrowing-hydrogen mechanism. The reaction begins with the dehydrogenation of the alcohol(s) to afford aldehydes, which subsequently undergo a condensation reaction with the nucleophile (aldehyde, ketone, or indole), followed by hydrogenation of the condensation product by Pt-H species to yield the desired product. In all of the methylation reactions explored in this study, the Pt/C catalyst exhibits a significantly higher turnover number than other previously reported homogeneous catalytic systems. Moreover, it is demonstrated that the high catalytic activity of Pt can be rationalized in terms of the adsorption energy of hydrogen on the metal surface, as revealed by density functional theory calculations on different metal surfaces.
- Siddiki, S. M. A. Hakim,Touchy, Abeda S.,Jamil, Md. A. R.,Toyao, Takashi,Shimizu, Ken-Ichi
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p. 3091 - 3103
(2018/04/14)
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- Photocatalytic Transfer Hydrogenolysis of Allylic Alcohols on Pd/TiO2: A Shortcut to (S)-(+)-Lavandulol
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We report herein a regio- and stereoselective photocatalytic hydrogenolysis of allylic alcohols to form unsaturated hydrocarbons employing a palladium(II)-loaded titanium oxide; the reaction proceeds at room temperature under light irradiation without stoichiometric generation of salt wastes. Olefin and saturated alcohol moieties tolerated the reaction conditions. Hydrogen atoms were selectively incorporated into less sterically congested carbons of the allylic functionalities. This protocol allowed a short-step synthesis of (S)-(+)-lavandulol from (R)-(?)-carvone by avoiding otherwise necessary protection/deprotection steps.
- Takada, Yuki,Caner, Joaquim,Kaliyamoorthy, Selvam,Naka, Hiroshi,Saito, Susumu
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supporting information
p. 18025 - 18032
(2017/12/08)
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- Regioselective Isomerization of 2,3-Disubstituted Epoxides to Ketones: An Alternative to the Wacker Oxidation of Internal Alkenes
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We report an alternative pathway to the Wacker oxidation of internal olefins involving epoxidation of trans-alkenes followed by a mild and highly regioselective isomerization to give the major ketone isomers in 66-98% yield. Preliminary kinetics and isotope labeling studies suggest epoxide ring opening as the turnover limiting step in our proposed mechanism. A similar catalytic system was applied to the kinetic resolution of select trans-epoxides to give synthetically useful selectivity factors of 17-23 for benzyl-substituted substrates.
- Lamb, Jessica R.,Mulzer, Michael,Lapointe, Anne M.,Coates, Geoffrey W.
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supporting information
p. 15049 - 15054
(2015/12/08)
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- Simple and clean synthesis of ketones from internal olefins using PdCl 2/N,N-dimethylacetamide catalyst system
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A simple catalytic system consisting of PdCl2 and N,N-dimethylacetamide enabled clean and selective synthesis of ketones from internal olefins using molecular oxygen. Various functionalized internal olefins were directly and regioselectively oxidized; C atoms of CC bonds far from substituted moieties were preferably oxidized.
- Mitsudome, Takato,Yoshida, Syuhei,Tsubomoto, Yamato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information
p. 1596 - 1598
(2013/03/14)
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- Air-stable, nitrile-ligated (cyclopentadienone)iron dicarbonyl compounds as transfer reduction and oxidation catalysts
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A series of air-stable, nitrile-ligated (cyclopentadienone)iron dicarbonyl compounds was synthesized and their activities as catalysts in the transfer reduction of acetophenone were explored. While all were active catalysts, the acetonitrile adduct was chosen for further study and was found to be active in the transfer reduction of aldehydes and ketones and in the Oppenauer-type oxidation of secondary alcohols. The acetonitrile catalyst exhibited activities similar to those of an analogous air-sensitive iron hydride, but unlike the iron hydride it was unreactive in carbonyl reductions using hydrogen gas. Copyright
- Plank, Taylor N.,Drake, Jessica L.,Kim, Daniel K.,Funk, Timothy W.
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supporting information; experimental part
p. 597 - 601
(2012/05/04)
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- Double hydroacylation reactions of acyclic and cyclic α,β- unsaturated aldehydes
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Double or quits? double hydroacylation reactions of acyclic and cyclic α,β-unsaturated aldehydes with olefins afford ketone and diketone products, respectively. Enantiomers are formed whose absolute configurations are controlled by the order of alkene addition.
- Cha, Kyung-Mi,Lee, Hyejeong,Park, Jung-Woo,Lee, Yura,Jo, Eun-Ae,Jun, Chul-Ho
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supporting information; experimental part
p. 1926 - 1930
(2011/10/17)
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- New platinum-catalysed dihydroalkoxylation of allenes
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A new platinum-catalysed dihydroalkoxylation of alienes is described to give aliphatic acetals by an unexpected attack of two molecules of methanol to the terminal carbon of the aliene moiety. Deuteration experiments suggest an unprecedented formal 1,3-dipolar addition of methanol to a zwitterionic platinum carbene as the key step. The first platinum-catalysed intermolecular carbonbased nucleophile addition to alienes is also reported.
- Munoz, Maria Paz,De La Torre, Maria C.,Sierra, Miguel A.
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supporting information; experimental part
p. 2189 - 2194
(2010/11/04)
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- Air-stable iron catalyst for the Oppenauer-type oxidation of alcohols
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An alcohol oxidation process using an air-stable iron tricarbonyl compound structurally similar to Shvo's diruthenium bridging hydride was developed. Secondary benzylic and allylic alcohols are oxidized in high yields, and evidence for an Oppenauer-type mechanism is presented.
- Moyer, Sara A.,Funk, Timothy W.
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experimental part
p. 5430 - 5433
(2010/10/20)
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- Tandem catalytic triple-bond cleavage of alkyne in association with aldehyde, alkene, and water
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In this tandem reaction the carbon-carbon triple bond of an alkyne is catalytically cleaved in association with aldehyde, al-kene, and H2O under catalyst mixtures of Rh(I), 2-amino-3-picoline, primary amine, and acid. The reaction starts with chelation-assisted hydroacylation of the alkyne with an aldehyde. The retro-Mannich-type fragmentation of the resulting ,α,β-unsaturated ketimine by an amine and acid affords a ketimine and an aldimine, which is trapped by an alkene and give ketones after hydrolysis. Georg Thieme Verlag Stuttgart.
- Cha, Kyung-Mi,Jo, Eun-Ae,Jun, Chul-Ho
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scheme or table
p. 2939 - 2942
(2010/01/21)
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- Expedient immobilization of TEMPO by copper-catalyzed azide-alkyne [3 + 2]-cycloaddition onto polystyrene resin
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TEMPO was readily grafted by copper(I)-catalyzed azide-alkyne cycloaddition onto polystyrene. Starting with commercially available Merrifield resin (4.3 mmol/g) almost quantitative loading of TEMPO onto the polymer was achieved (≥ 4 mmol/g). The so obtained PS-CLICK-TEMPO allowed the oxidation of alcohols to aldehydes with bleach or molecular oxygen as the terminal oxidant with high yields and selectivity in multiple cycles without loss of activity.
- Gheorghe, Alexandru,Matsuno, Ai,Reiser, Oliver
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p. 1016 - 1020
(2007/10/03)
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- Ozonolysis of ricinolic acid derivatives and transformations of the ozonolysis products under barton reaction conditions
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The possibility of functionalizing the alkyl part of ricinolic acid using the Barton reaction was investigated.
- Ishmuratov,Kharisov,Shayakhmetova,Botsman,Shitikova,Tolstikov
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p. 643 - 649
(2008/02/01)
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- Investigations of the scope and mechanism of the tandem hydroesterification/lactonization reaction
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(Chemical Equation Presented) Heating allylic and homoallylic alcohols and 2-pyridylmethyl formate in the presence of Ru3(CO)12 initiates a tandem sequence of hydroesterification and lactonization. Mechanistic studies suggest that regioselectivity and overall reaction efficiency are governed by the relative rates of reductive elimination and β-hydride elimination for the alkylruthenium intermediates.
- Wang, Lijun,Floreancig, Paul E.
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p. 4207 - 4210
(2007/10/03)
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- Desilylation and conversion of trimethylsilylmethyl epoxides into ketones under the influence of a bulky base
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Trimethylsilylmethyl epoxides were converted into ketones through a desilylation, epoxide ring-opening, and rearrangement reaction under the influence of a bulky base in the presence of 18-crown-6.
- Ma, Yuan
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p. 310 - 315
(2007/10/03)
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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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- 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 methods of hydroformylation of olefins and isomerisation of allyl alcohols using the CoBr2/Zn/CO/t-BuOH reagent system
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The reaction of CoBr2/Zn/CO/t-BuOH gives cobalt carbonyl species that is useful for the hydroformylation of olefins to obtain corresponding aldehydes. The cobalt carbonyl species formed is also useful in isomerisation of allyl alcohols to the corresponding ketones.
- Rajesh,Periasamy
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p. 989 - 993
(2007/10/03)
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- Cascade rearrangement of spiroepoxymethyl radicals into 2-oxocycloalkyl radicals: Evaluation of a two-carbon cycloalkanone ring expansion
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Series of 2-bromomethyl- and 2-hydroxymethyl-1-oxaspiro[2.n]alkanes were prepared from cycloalkanones by initial Wadsworth-Horner-Emmons methodology to afford ester-substituted methylenecycloalkanes. The latter were selectively reduced to hydroxymethylmethylenecycloalkanes which were epoxidised with peroxyacetic acid. Homolytic reactions were studied by EPR spectroscopy which enabled transient 3-oxoalk-1-enyl radicals, and their cyclisation products, 2-oxocycloalkyl and 2-oxocycloalkylmethyl radicals, to be characterised. This evidence, together with end product analyses of organotin hydride reductions of the 2-bromomethyl-1-oxaspiro[2.n]alkanes, established that the initial spiroepoxymethyl radicals rearranged by a three-stage cascade of two consecutive β-scissions followed by a cyclisation. Cyclisations of the 3-oxoalk-1-enyl radicals took place mainly in the endo-mode to afford 2-oxocycloalkyl radicals, except for the 5-oxohept-6-enyl radical for which exo-cyclisation to generate the 2-oxocyclohexylmethyl radical was preferred. Kinetic data for the exo-and endo-cyclisations of the 4-oxohex-5-enyl radical were obtained from tributyltin hydride mediated reactions of 2-bromomethyl-1-oxaspiro[2.3]hexane.
- Afzal, Mohammad,Walton, John C.
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p. 937 - 945
(2007/10/03)
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- A New Method for the Synthesis of gem-Dihydroperoxides
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The tungstic acid-catalysed reaction of ketals with hydrogen peroxide provides a convenient and efficient method for preparing gem-dihydroperoxides.
- Jefford, Charles W.,Li, Yun,Jaber, Amer,Boukouvalas, John
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p. 2589 - 2596
(2007/10/02)
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- A New Synthetic Method for the Preparation of Ketones by Denitration of α-Nitro Ketones
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The sequence of acylation of nitroalkanes and subsequent denitration of the resulting α-nitro ketones provides a new and general method for the preparation of ketones.
- Ono, Noboru,Fujii, Masayuki,Kaji, Aritsune
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p. 532 - 535
(2007/10/02)
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- α,β-Epoxy Sulfoxides as Useful Intermediates in Organic Synthesis. I. A Novel Synthesis of Dialkyl Ketones and a Synthesis of Aldehydes from Ketones by One Carbon Elongation
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Treatment of α,β-epoxy sulfoxides, prepared from 1-chloroalkyl phenyl sulfoxides with ketones or aldehydes, with sodium benzeneselenolate gives dialkyl ketones or aldehydes in good yields under mild conditions.The mechanism of this reaction and an application of this process to a formal total synthesis of dihydrojasmone are described.
- Satoh, Tsuyoshi,Kaneko, Youhei,Izawa, Takao,Sakata, Kiichi,Yamakawa, Koji
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p. 1983 - 1990
(2007/10/02)
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- A VERSATILE ACCESS TO UNSYMMETRICAL AND SYMMETRICAL α-DIKETONES VIA ORGANOTIN REAGENTS
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Unsymmetrical α-diketones have been obtained via cross coupling of acyltins with acyl halides under PdCl2(PPh3)2 catalysis while symmetrical α-diketones have been readily obtained via "in situ" formation of acyltins using hexabutylditin and acyl chlorides under similar experimental conditions.
- Verlhac, Jean-Baptiste,Chanson, Evelyne,Jousseaume, Bernard,Quintard, Jean-Paul
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p. 6075 - 6078
(2007/10/02)
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- Low Temperature Free-Radical Reactions Initiated with tert-Butyl p-Benzoylperbenzoate. Selective Acyl Radical Additions to Substituted Olefins
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Competition experiments involving acyl radical additions to simple and electron-deficient olefins showed a definite preference for acylation of the latter olefin.This selectivity was significantly enhanced by using low temperature initiation with tert-butyl p-benzoylperbenzoate (1), which allows selective initiation of free-radical cyclization reactions that have synthetic importance.
- Gottschalk, Peter,Neckers, D. C.
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p. 3498 - 3502
(2007/10/02)
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- REGIO- AND STEREODEFINED SYNTHESIS OF TRIMETHYLSILYL ENOL ETHERS RESULTED FROM THE ISOMERIZATION OF α-TRIMETHYLSILYL KETONES
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The isomerization of an α-trimethylsilyl ketone is lead to the corresponding trimethylsilyl enol ether with the enhanced regioselectivity by heating or by the assist of trimethylsilyl trifluoromethanesulfonate.The thermal reaction discloses a new regiodefined (E)-selective route to silyl enol ethers.
- Matsuda, Isamu,Sato, Susumu,Hattori, Motoaki,Izumi, Yusuke
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p. 3215 - 3218
(2007/10/02)
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- PALLADIUM CHLORIDE AND POLYETHYLENE GLYCOL PROMOTED OXIDATION OF TERMINAL AND INTERNAL OLEFINES
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Both terminal and internal olefins can be efficiently converted to ketones in polyethylene glycol and water using palladium chloride as the catalyst.
- Alper, Howard,Januszkiewicz, Krysztof,Smith, David J. H.
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p. 2263 - 2264
(2007/10/02)
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- A NOVEL SYNTHESIS OF DIALKYL KETONES AND α-SULFENYLATED CARBONYL COMPOUNDS FROM α,β-EPOXY SULFOXIDES
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Treatment of α,β-epoxy sulfoides with excess sodium phenylselenide and various kinds of alkylthiolates gave dialkyl ketones and α-sulfenylated carbonyl compounds, respectively, in good yields under mild conditions.
- Satoh, Tsuyoshi,Kaneko, Youhei,Kumagawa, Takumi,Izawa, Takao,Sakata, Kiichi,Yamakawa, Koji
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p. 1957 - 1960
(2007/10/02)
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- A NEW SYNTHESIS OF KETONES FROM 1,2-DIMETHOXYETHENYLLITHIUM, ORGANOBORANES, AND ALKYL FLUOROSULFONATES
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The reaction of alkyl fluorosulfonates with lithium 1,2-dimethoxyethenyltrialkylborates readily prepared from organoboranes gives corresponding ketones in good yields.
- Yogo, Toshinobu,Koshino, Junji,Suzuki, Akira
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p. 1059 - 1060
(2007/10/02)
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