Stereoselective epoxidation of allylic alcohols and dehydrogenative oxidation of secondary alcohols by means of t-butyl hydroperoxide and aluminium reagents.

スポンサーリンク

概要

• 論文の詳細を見る

• Treatment of a solution of geraniol and (<I>t</I>-BuO)<SUB>3</SUB>Al in benzene with <I>t</I>-BuOOH at 5 °C gives (2<I>R</I><SUP>*</SUP>, 3<I>R</I><SUP>*</SUP>)-2,3-epoxy-3,7-dimethyl-6-octenyl acetate in 83% yield after acetylative workup. Eight allylic alcohols are converted to α,β-epoxy alcohols in preparative yields. The epoxidation of secondary (<I>E</I>)-allylic alcohols shows opposite stereoselectivities to <I>t</I>-BuOOH–VO(acac)<SUB>2</SUB> system. Asymmetric epoxidation with a chiral hydroxamic acid as a ligand gives unsatisfactory degrees of enantiomeric excess. The same system can also convert secondary alcohols into ketones in excellent yields, while primary ones react very slowly.

• 公益社団法人 日本化学会の論文

著者

• Takai Kazuhiko

  Department Of Applied Chemistry Faculty Of Engineering Okayama University

• Nozaki Hitosi

  Department of Industrial Chemistry, Faculty of Engineering Kyoto University

• Oshima Koichiro

  Department of Chemistry, Massachusetts Institute of Technology

関連論文

• Improved Synthesis and Crystal Structure of TiCl_3 (tmeda) (thf): A Highly Stereoselective Pinacol Coupling Reagent for Aromatic Aldehydes
• Copper-Catalyzed Arylation of Chlorosilanes with Grignard Reagents
• Palladium-catalyzed Mizoroki-Heck Reactions of 2-Methylene-1,3-dithiane 1-Oxide with Aryl Iodides
• Synthesis of β,γ-Unsaturated Ketones from Acid Chlorides through Carbon-Pentamethylcyclopentadienyl Bond Formation and Cleavage
• Synthesis of Prenylarenes and Related (Multisubstituted Allyl)arenes from Aryl Halides and Homoallyl Alcohols via Palladium-Catalyzed Retro-Allylation
• Manganese-catalyzed Phenylation of Acetylenic Compounds with a Phenyl Grignard Reagent
• Preparation of Deuterium Labelled Organophosphonium Salts (Wittig Salts) under Hydrothermal Condition Catalyzed by Molecular Sieves
• Trialkylmanganate Mediated Radical Addition of Triphenylgermane to Carbon-Carbon Multiple Bonds
• Ruthenium-catalyzed Isomerization of Alkenol into Alkanone in Water under Irradiation of Microwaves
• Radical Addition of α-Halo Ester to Homoallylic Gallium or Indium Species : Formation of Cyclopropane Derivatives
• Allylation of Carbonyl Compounds with Allylic Gallium Reagents
• Preparation of Organoytterbium Reagent from Ytterbium Trichloride and Organomagnesium
• Stereoselective Allylation of 3-Oxo Amides
• Ruthenium Catalyzed Deuterium Labelling of α-Carbon in Primary Alcohol and Primary/Secondary Amine in D_2O
• Palladium-Catalyzed H-D Exchange Reaction under Hydrothermal Condition
• S_N2 Type Hydrolysis of Secondary Alkyl Halides and Sulfonates in Hydrothermal Water
• Synthesis of Coordinatively Unsaturated Cobalt(II)-Alkyl Complexes Bearing Phosphorus-bridged [1.1]Ferrocenophanes
• Facile Preparation of Vicinal Allylsiloxy-and Vinylsiloxyhaloalkanes and Their Radical Cyclization Reaction
• Selective Cyclotrimerization of Acetylenes via Tantalum-Alkyne Complexes
• Alkylidenation of Ketones by gem-Dibromoalkane, SmI_2, and Sm in the Presence of Catalytic Amount of CrCl_3
• Ytterbium Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Means of Iodosylbenzene
• Tris(trimethylsilyl)silyl Radical Induced Bicyclization of 1,6-Dienes and 1,6-Enynes Providing 3,3-Bis(trimethylsilyl)-3-silabicyclo[3.3.0]octanes and 3-Silabicyclo[3.3.0]oct-1-enes
• 2-Lithio-2-trimethylsilyl-1-silacyclopentane as a Synthetic Equivalent of 1-Lithio-1,4-butanediol
• Radical Addition of Polyhaloalkanes to 2-Ethynyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• Radical Addition of Alkyl Halides to 2-Methylene-1,3-dithiane Monoxide as a Ketene Equivalent
• Extended Pummerer Reaction of Arylketene Dithioacetal Monoxides with Aromatic Compounds by Means Trifluoromethanesulfonic Anhydride
• Triethylborane-Induced Radical Reaction of Alkynylgallium with α-Halo Carbonyl Compounds
• Triethylborane Induced Radical Reaction of Gallium Enolates with α-Halo Esters
• Wittig Type Methylenation of Ketones with Bis(iodozincio)methane and Ionic Liquid
• The Rate Enhancement Effect of Protodesilylation of Arylsilane Derivatives
• Fabrication of Nano-structure by Diels-Alder Reaction
• Synthesis of Pyrimidines via Base-induced Condensation of α-Chloro Oxime Derivatives
• Cobalt-catalyzed Cross-coupling Reactions of Aryl Bromides with Alkyl Grignard Reagents
• Regio- and Stereoselective Additions of Diphenyldithiophosphinic Acid to N-(1-Alkynyl)amides and 1-Alkynyl Sulfides
• Silylcupration and Copper-Catalyzed Carbomagnesiation of Ynamides : Application to Aza-Claisen Rearrangement
• Regio- and Stereoselective Hydrothiolation Reactions of Ynamides with Diphenyldithiophosphinic Acid : Straightforward Synthesis of Ketene N,S-Acetal Derivatives
• Transformations of N-Allyl-N-(phenylethynyl)arenesulfonamides into 2,2-Disubstituted 4-Pentenenitriles through Aza-Claisen Rearrangement that Follows Carbomagnesiation
• Cobalt-Catalyzed Allylzincations of Internal Alkynes
• Rhodium-Catalyzed Reaction of 1-Alkynylphosphines with Water Yielding (E)-1-Alkenylphosphine Oxides
• Atom-transfer Radical Addition of α-Iodo Esters to 1-Alkynyl Sulfides
• Palladium-Catalyzed 1-Methylene-2-propenylation Reactions of Aryl Bromides with 3,4-Alkadien-1-ols via Carbon-Carbon Bond Cleavage for the Synthesis of 2-Aryl-1,3-butadiene Derivatives
• Efficient Aerobic Oxidation of Phosphines, Phosphites, and Sulfides by Using Trialkylborane
• Nickel-catalyzed Carbometalation Reactions of [2-(1-Propynyl)phenyl]methanol with 1-Alkenylmagnesium Reagents
• Cobalt-catalyzed Cross-coupling Reaction of Chloropyridines with Grignard Reagents
• Reaction of Tantalum-Alkyne Complexes with Hydrazones. Stereoselective Synthesis of (E)-Allylic Hydrazines.
• Catalytic Performance of Tantalum-η^2-Alkyne Complexes [TaCl_3(R^1C≡CR^2)L_2] for Alkyne Cyclotrimerization
• Successive Carbon-Carbon Bond Formation by Sequential Generation of Radical and Anionic Species with Manganese and Catalytic Amounts of PbCl_2 and Me_3 SiCl
• Nucleophilic addition of organochromium reagents to carbonyl compounds
• Transformation of Aldehydes into (E)-1-Alkenylsilanes and (E)-1-Alkenylboronic Esters with a Catalytic Amount of a Chromium Salt
• Teritary Amine-Accelerated Allylgallation of Terminal Alkynes
• Activation of Manganese Metal with a Catalytic Amount of Lead and Me_3SiCl and Its Application to Organic Synthesis
• Thiocarbonyl Ylides. Attempted Preparation and Related Reactions
• Preparative and Structural Studies of Kostanecki's Compound
• The Reduction of gem-Dibromocyclopropanes by Means of Chromium(II) Acetate or Potassium Pentacyanocobaltate
• Regiocontrolled formation of 4,5-dihydro-3(2H)-furanones from 2-butyne-1,4-diol derivatives. Synthesis of bullatenone and geiparvarin.
• Highly selective carbon-carbon bond forming reactions mediated by chromium(II) reagents.
• Cross-coupling reaction between enol phosphates and organoaluminium compounds in the presence of palladium(0) catalyst.
• The Reaction of Styryl Sulfoxides or Sulfones with Boranes
• Reaction of organoaluminium reagents with cyclopropylmethyl acetates and 2-vinylcyclopropane-1,1-dicarboxylate esters.
• 1-Bromo-2-ethoxycyclopropyllithium: A synthetic equivalent of 2-lithio- or 3-lithiopropenal. Application to the synthesis of juvenile hormone (JH-II), .BETA.-sinensal, and jasmonoids.
• A novel synthesis of .ALPHA.-methylene-.GAMMA.-butyrolactones.
• Isomerization of allylic alcohols catalyzed by vanadium or molybdenum complexes.
• Reformatsky type reaction with new aluminium reagents containing Al-Sn or Al-Pb linkage.
• New methods for the synthesis of 3(2H)-furanones and 2(5H)-furanones.
• Alkylation of bromocyclopropanes and bromoarenes by means of dibutylcopperlithium and alkyl halides.
• A facile ring enlargement reaction via .BETA.-oxido carbenoid.
• The Reaction of Ethyl Azidoformate with Electron Deficient Olefins and the Thermal Ring Opening of the Resulting Aziridines.
• The Photolysis and Thermolysis of Ethyl Azidoformate in the Presence of Ketones
• A practical synthesis of polyhalomethyllithium-carbonyl adducts.
• Abnormal nazarov reaction. A new synthetic approach to 2,3-disubstituted 2-cyclopentenones.
• Tungsten hexachloride-catalyzed decomposition of diazo compounds. A novel oxazole synthesis.
• Condensation Reactions of Sulfonylcarbanion
• Synthesis and Reactions of Sulfonium Diacylmethylide Having Active Hydrogen
• Intramolecular cyclization of nerol and the related attack of (Z)-allylic alcohol moiety on the terminal olefin linkage as induced by TiCl4-PhNHMe complex. Synthesis of nezukone.
• The Nucleophilic Cyclopropylation of the Condensed Aromatic Ring with Sulf onylcarbanion
• Stereochemical studies on the nucleophilic substitution in the reaction of allylic phosphates with organoaluminum reagents.
• Synthesis of [9]Heterophanes from 2-Cyclododecenone
• Carbocyclic ring formation by the intramolecular reaction between enol silyl ether and allylic acetate moieties.
• Synthesis of homoallylic alcohols from allylic phosphates and aldehydes with organoaluminum reagent containing Al-Sn linkage.
• The 1-Methylene Derivatives of [7](2,6)Pyridinophane. Preparative and Conformational Studies
• The Absolute Configurations of 2-Phenylaziridine and Its Derivatives
• Thermolysis and Photolysis of Benzopinacol Dicarboxylates
• The Reaction of O,O′-Diethyl α-Lithiomethylphosphonate with Organic Dihalides
• The Oxidation of Alkylbenzenes and Acylcarbinols by Means of Benzopinacol Diesters
• Cyclopentenone synthesis from 1,1-dichloroallyllithium-ketone adducts as well as from dichlorocarbene-allyl alcohol adducts.
• The Dehalogenation of Organic Halides by Means of Iron(II) Chloride in Dimethyl Sulfoxide
• Rearrangement of vic-diol monoacetates promoted by organoaluminium compounds.
• Stereoselective epoxidation of allylic alcohols and dehydrogenative oxidation of secondary alcohols by means of t-butyl hydroperoxide and aluminium reagents.
• Baeyer-Villiger oxidation with Me3SiOOSiMe3 under assistance of SnCl4 or BF3OEt2.
• Chromium(VI) or ruthenium(II) complex catalysis in oxidation of alcohols to aldehydes and ketones by means of bis(trimethylsilyl) peroxide.
• Aliphatic Claisen rearrangement promoted by organoaluminium reagents.
• The Syntheses and Reactions of Sulfenyl-substituted Sulfonium Ylides
• The Acid-Catalyzed Ring-Opening of Cyclooctenimine Derivatives
• Cr(III) or Ce(IV) impregnated perfluorinated resin-sulfonic acid catalyst for the oxidation of alcohols.
• A New Synthesis of Thiophenes
• Photoinduced Transannular Reaction of 4,5-Octamethylene-1,3-dioxolen-2-one
• The Reaction of Acyl-substituted Sulfonium and Pyridinium Ylides with Diphenylthiirene Dioxide
• Palladium-catalyzed ketone synthesis from acyl chloride and organoaluminum reagents.
• Preparation of 2-alkenylsilanes and 2-alkenylstannanes by the reaction of 2-alkenyl-1,1-cyclopropanedicarboxylate esters with PhMe2SiAlEt2 and (Ph3Sn)2Zn. Generation of 2-alkenyl-3-cyclopentene-1,1-decarboxylates via alkenyl-substituted .PI.-allylpalladiu
• Photochemistry of Non-enolizable β-Diketones Containing Cyclopropane Ring in Conjugation

もっと見る 閉じる

スポンサーリンク