107-88-0Relevant articles and documents
-
Covert,Adkins
, p. 4117 (1932)
-
Chemical Aspects of Electrocatalytic Reduction of Carbonyl Compounds. Aldehydes
Shchelkunov,Do,Bekenova,Shchelkunov
, p. 735 - 735 (2003)
-
Hydroboration. 71. Hydroboration of Representative Heterocyclic Olefins with Borane-Methyl Sulfide, 9-Borabicyclononane, Dicyclohexylborane, and Disiamylborane. Synthesis of Heterocyclic Alcohols
Brown, Herbert C.,Prasad, J. V. N. Vara,Zee, Sheng-Hsu
, p. 1582 - 1589 (1985)
The hydroboration of representative heterocycles bearing an endocyclic double bond with borane-methyl sulfide (BMS), 9-borabicyclononane (9-BBN), dicyclohexylborane (Chx2BH), and disiamylborane (Sia2BH) was investigated systematically to establish the optimum conditions for the clean and quantitative hydroboration.The hydroboration of 2,3- and 2,5-dihydrofurans with BMS (3:1 molar ratio) at 25 deg C for 1 h affords the trialkylborane, readily oxidized to 3-hydroxytetrahydrofuran in excellent yield.However, preparation of the corresponding dialkylboranes from these olefins using 2 olefin/BMS was not possible even at 0 deg C.Excess hydride and prolongated reaction time cause ring cleavage of the alkylboranes to yield both unsaturated alcohol and the dihydroborated products 1,3- and 1,4-pentanediols.Hydroboration of both 2,3-dihydrothiophene and 2-methyl-4,5-dihydrofuran with BMS proceeds cleanly to the trialkylborane stage, oxidized to the corresponding alcohols in almost quantitative yields.Hydroboration of 3-pyrroline with BMS could not be achieved with the unprotected nitrogen atom.Such hydroboration could be accomplished by protecting the nitrogen atom with the benzyloxycarbonyl group affording the trialkylborane, readily converted to N-(benzyloxycarbonyl)-3-pyrrolidinol in good yield.Conditions for a clean hydroboration of these heterocyclic five-membered olefins with 9-BBN, Chx2BH, and Sia2BH were also established.In all cases clean trialkylboranes were obtained, readily oxidized to heterocyclic alcohols in high yields. 3,4-Dihydropyran, on hydroboration with BMS, followed by oxidation, affords 3-hydroxytetrahydropyran in good yield.However, ring cleavage in this case is greater when compared to 2,3-dihydrofuran. 2-Methoxy- or 2-ethoxy-3,4-dihydro-2H-pyran readily undergo hydroboration with BMS to the trialkylboranes, oxidized to the corresponding trans and cis alcohols in a 7:3 ratio.As the steric requirements of the dialkylborane are increased, more trans alcohol is formed.Thus at 0 deg C, the ratios of trans to cis alcohols were increased from 1:1 to 7:3 and then to 8:2 with 9-BBN, Chx2BH, and Sia2BH, respectively.N-(Benzyloxycarbonyl)-1,2,3,6-tetrahydropyridine is readily hydroborated with BMS, 9-BBN, Chx2BH, and Sia2BH to the corresponding trialkylboranes, readily oxidized to N-(benzyloxycarbonyl)-3- and -4-piperidinols in good yield.Strongly basic groups in the heterocyclic ring can greatly reduce the ease of hydroboration, and the introduction of boron β to the heteroatom can lead to elimination.However, both problems can be avoided to provide ready hydroboration-oxidation of heterocyclic olefins.
A Chemoselective One-Step Reduction of β-Ketoesters to 1,3-Diols
Soai, Kenso,Oyamada, Hidekazu
, p. 605 - 607 (1984)
-
Selective hydrogenolysis of polyols and cyclic ethers over bifunctional surface sites on rhodium-rhenium catalysts
Chia, Mei,Pagan-Torres, Yomaira J.,Hibbitts, David,Tan, Qiaohua,Pham, Hien N.,Datye, Abhaya K.,Neurock, Matthew,Davis, Robert J.,Dumesic, James A.
, p. 12675 - 12689 (2011)
A ReOx-promoted Rh/C catalyst is shown to be selective in the hydrogenolysis of secondary C-O bonds for a broad range of cyclic ethers and polyols, these being important classes of compounds in biomass-derived feedstocks. Experimentally observed reactivity trends, NH3 temperature-programmed desorption (TPD) profiles, and results from theoretical calculations based on density functional theory (DFT) are consistent with the hypothesis of a bifunctional catalyst that facilitates selective hydrogenolysis of C-O bonds by acid-catalyzed ring-opening and dehydration reactions coupled with metal-catalyzed hydrogenation. The presence of surface acid sites on 4 wt % Rh-ReOx/C (1:0.5) was confirmed by NH3 TPD, and the estimated acid site density and standard enthalpy of NH3 adsorption were 40 μmol g-1 and -100 kJ mol-1, respectively. Results from DFT calculations suggest that hydroxyl groups on rhenium atoms associated with rhodium are acidic, due to the strong binding of oxygen atoms by rhenium, and these groups are likely responsible for proton donation leading to the formation of carbenium ion transition states. Accordingly, the observed reactivity trends are consistent with the stabilization of resulting carbenium ion structures that form upon ring-opening or dehydration. The presence of hydroxyl groups that reside α to carbon in the C-O bond undergoing scission can form oxocarbenium ion intermediates that significantly stabilize the resulting transition states. The mechanistic insights from this work may be extended to provide a general description of a new class of bifunctional heterogeneous catalysts, based on the combination of a highly reducible metal with an oxophilic metal, for the selective C-O hydrogenolysis of biomass-derived feedstocks.
ZnCl2-catalyzed hydrodefluorination of gem-difluoromethylene derivatives with lithium aluminum hydride
Cheng, Jianhang,Wu, Jingjing,Cao, Song
, p. 3481 - 3484 (2011)
Hydrodefluorination of gem-difluoromethylene derivatives with lithium aluminum hydride in the presence of a catalytic amount of ZnCl2 in good to high yields was described. A possible mechanism is also suggested.
Non-catalytic conversion of C-F bonds of gem-difluoromethylene derivatives to C-H bonds with lithium aluminum hydride under room temperature
Wu, Jing-Jing,Cheng, Jian-Hang,Zhang, Jian,Shen, Li,Qian, Xu-Hong,Cao, Song
, p. 285 - 288 (2011)
An unexpected hydrodefluorination of unactivated aliphatic C-F bonds of CF2 derivatives with LiAlH4 at room temperature without any added metal catalyst was reported. Deuterium-labeling experiments suggested that the hydrogens introduced into the products originated from LiAlH 4. Copyright
Novel Catalytic Oxidation of Terminal Olefins by Cobalt(II)-Schiff Base Complexes
Zombeck, Alan,Hamilton, Dorothy E.,Drago, Russell S.
, p. 6782 - 6784 (1982)
-
Directing activator-assisted regio- and oxidation state-selective aerobic oxidation of secondary C(sp3)-H bonds in aliphatic alcohols
Ni, Jizhi,Ozawa, Jun,Oisaki, Kounosuke,Kanai, Motomu
, p. 4378 - 4381 (2016)
The regioselective conversion of an unactivated C(sp3)-H bond of a methylene carbon (CH2) into a C-O single bond is an attractive reaction in organic synthesis. Herein, we present a strategy for a regio- and oxidation state-selective aerobic C-H oxidation based on an N-hydroxyamide-derived directing activator (DA), which is attached to a hydroxy group in alcohol substrates. The DA reacts with NOx species generated in situ from NaNO2, a Br?nsted acid, and aerobic oxygen, and effectively generates an amidoxyl radical from the N-hydroxy moiety of the DA. Then, the amidoxyl radical promotes site-selective intramolecular C-H abstraction from methylenes with γ- (or δ-) selectivity. The thus-generated methylene radicals are trapped by molecular oxygen and NO. This process results in the predominant formation of nitrate esters as products, which suppresses undesired overoxidation. The products can be easily converted into alcohols after hydrogenolysis.
METHOD FOR PRODUCING ALCOHOL
-
Paragraph 0104; 0106, (2022/02/05)
The present invention provides a method for selectively producing an alcohol by efficiently hydrogenating a lactone. The present invention is a method for producing an alcohol, the method including hydrogenating a substrate lactone represented by Formula (1), in the presence of a catalyst described below, to produce an alcohol that is represented by Formula (2). In the formulae, R represents a divalent hydrocarbon group which may have a hydroxyl group. The catalyst comprises: metal species including M1 and M2; and a support supporting the metal species, and wherein M1 is rhodium, platinum, ruthenium, iridium, or palladium; M2 is tin, vanadium, molybdenum, tungsten, or rhenium; and the support is hydroxyapatite, fluorapatite, hydrotalcite, or ZrO2.
METHOD FOR PRODUCING 1,3-BUTANEDIOL
-
Paragraph 0046-0049, (2021/04/23)
PROBLEM TO BE SOLVED: To achieve high conversion rates and selectivity coefficients in producing 1,3-butanediol by performing the hydrogenation of acetaldol obtained by the condensation of acetaldehyde. SOLUTION: A method for producing 1,3-butanediol includes hydrogenating acetaldol with a hydrogen gas, using a hydrogenation catalyst. From a reaction solution after hydrogenation, a low-boiling component of a reaction by-product is separated and collected, and all or part of the low-boiling component is used to dilute acetaldol as raw material, after which hydrogenation is performed. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
supporting information, p. 5665 - 5679 (2021/08/16)
The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
