820-29-1Relevant articles and documents
Ruthenium-on-Carbon-Catalyzed Facile Solvent-Free Oxidation of Alcohols: Efficient Progress under Solid-Solid (Liquid)-Gas Conditions
Park, Kwihwan,Jiang, Jing,Yamada, Tsuyoshi,Sajiki, Hironao
, p. 1200 - 1205 (2021/12/29)
A protocol for the ruthenium-on-carbon (Ru/C)-catalyzed solvent-free oxidation of alcohols, which proceeds efficiently under solid-solid (liquid)-gas conditions, was developed. Various primary and secondary alcohols were transformed to corresponding aldehydes and ketones in moderate to excellent isolated yields by simply stirring in the presence of 10% Ru/C under air or oxygen conditions. The solvent-free oxidation reactions proceeded efficiently regardless of the solid or liquid state of the substrates and reagents and could be applied to gram-scale synthesis without loss of the reaction efficiency. Furthermore, the catalytic activity of Ru/C was maintained after five reuse cycles.
Selective Visible Light Aerobic Photocatalytic Oxygenation of Alkanes to the Corresponding Carbonyl Compounds
Somekh, Miriam,Khenkin, Alexander M.,Herman, Adi,Neumann, Ronny
, p. 8819 - 8824 (2019/09/30)
The aerobic, selective oxygenation of alkanes via C-H bond activation is an important research challenge. Photocatalysis offers the potential for the introduction of additional concepts for such reactions. Visible light photoactive semiconductors such as bismuth oxyhalides (BiOX, X = Cl and Br) used in this research typically oxidize organic compounds through photocatalyzed formation of strongly oxidizing holes. The reactive oxygen species formed react with organic compounds in one-electron processes, leading to radical intermediates and nonselective oxidation. Such oxidation reactions generally lead to total oxidation. Here, impregnation of BiOX with a polyoxometalate, H5PV2Mo10O40, as a strong electron acceptor changed the reactivity of BiOX, leading to Mars-van Krevelen-type reactivity, that is, photoactivated oxygen donation from BiOX to the organic substrate followed by reoxidation by O2 and catalysis. This conclusion was supported by mechanistic studies involving isotope labeling studies. In this way, ethane was selectively oxidized to acetaldehyde in a flow reactor with a turnover number (24 h) of 415.
Internal Alkyne Regio- and Chemoselectivity using a Zwitterionic N-Heterocyclic Carbene Gold Catalyst in a Silver-Free Alkyne Hydration Reaction
Weerasiri, Kushan C.,Chen, Danmin,Wozniak, Derek I.,Dobereiner, Graham E.
, p. 4106 - 4113 (2016/12/30)
An alkyne hydration of terminal and internal alkynes is reported using a zwitterionic N-heterocyclic carbene gold catalyst [(BNHC)Au(SMe2)] in the absence of silver and Br?nsted acid additives. The hydration demonstrates good regioselectivity in alkyne hydration and chemoselectivity for internal alkynes vs. terminal. In addition, (BNHC)Au(SMe2) performs a propargyl alcohol hydration to predominantly form α-hydroxymethyl ketone over the more common Meyer–Schuster rearrangement product. While complex (BNHC)Au(SMe2) is active without silver additives, addition of silver hexafluoroantimonate (AgSbF6) increases reaction rate and decreases selectivity for internal alkyne hydration over terminal substrates. To the best of our knowledge, the rate enhancement of (BNHC)Au(SMe2) by AgSbF6is the first such demonstration of a silver effect for a “halide-free” Au catalyst. (Figure presented.).
Silver-containing microemulsion as a high-efficient and recyclable catalytic system for hydration of alkynes
Dong, Qizhi,Li, Ningbo,Qiu, Renhua,Wang, Jinying,Guo, Cancheng,Xu, Xinhua
, p. 122 - 127 (2015/10/12)
A silver-catalyzed highly efficient and regioselective synthesis of ketones from a wide range of alkynes is described. The reaction is dramatically accelerated by its performance in aqueous emulsion, which is self-assembled by the addition of silver perfluorooctanesulfonate (1) and perfluorooctanesulfonic acid (PFOS) to water. The reaction is conducted under convenient conditions with broad substrate scope, including a variety of aromatic and aliphatic terminal alkynes and internal alkynes. Furthermore, the air- and light-stable silver catalytic microemulsion can be reused for 4 times with minimal change in catalytic efficiency.
Carbonylative enantioselective meso-desymmetrization of cis-epoxides to trans-β-lactones: Effect of salen-ligand electronic variation on enantioselectivity
Mulzer, Michael,Lamb, Jessica R.,Nelson, Zachary,Coates, Geoffrey W.
supporting information, p. 9842 - 9845 (2014/08/18)
Carbonylation catalysts for the desymmetrization of meso-epoxides yielding enantioenriched trans-β-lactones are reported. Fine-tuning the electronic properties of the ligand further improved enantioselectivity. The sterics of the substrate dictated whether a given electronic variation decreased or increased enantioenrichment, revealing an unexpected relationship between the substrate's steric environment and the electronic nature of the optimal catalyst.
Mild and direct conversion of esters to morpholine amides using diisobutyl(morpholino)aluminum: Application to efficient one-pot synthesis of ketones and aldehydes from esters
Jeon, Ah Ram,Kim, Min Eai,Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
, p. 4420 - 4424 (2014/06/10)
Morpholine amide intermediates, which are easily prepared by aminolysis of various esters with diisobutyl(morpholino)aluminum, react with organolithium and reducing agents (DIBALH or LDBMA) without isolation of the aminolysis intermediates to give ketones in 83-95% yields and aldehydes quantitatively.
An effective one-pot conversion of acid chlorides to aldehydes and ketones
Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
, p. 3199 - 3203 (2013/06/27)
Aldehydes and ketones were synthesized from their respective acid chlorides via a one-pot protocol. Morpholine amide intermediates that were readily prepared by the aminolysis of various acid chlorides with diisobutyl(morpholino) aluminum smoothly reacted with the reducing agent LDBMA and the organolithium reagents under mild reaction conditions (0 C), giving almost excellent product yields of up to 95%.
METHOD FOR MANUFACTURING KETONE
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Page/Page column 7, (2011/12/12)
A method for manufacturing a ketone includes oxidizing an internal olefin or a cyclic olefin having one carbon-carbon double bond or more at a position other than terminals of a molecule thereof in an amide-based solvent in the presence of water, a palladium catalyst, and molecular oxygen, thereby bonding an oxo group to at least one of the carbon atoms constituting the carbon-carbon double bond, in which the amide-based solvent is represented by the formula in the formula (1), R1 represents an alkyl group having 1 to 4 carbon atoms, R2 and R3 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group, and when R1 and R2 are alkyl groups, R1 and R2 may be bonded to each other to form a ring structure.
KETONE MANUFACTURING METHOD
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Page/Page column 9-10, (2011/10/04)
A method for manufacturing a ketone comprising: oxidizing an internal olefin or a cyclic olefin having one carbon-carbon double bond or more at a position other than terminals of a molecule thereof in an amide-based solvent in the presence of water, a palladium catalyst, and molecular oxygen, thereby bonding an oxo group to at least one of the carbon atoms constituting the carbon-carbon double bond, the amide-based solvent being represented by the following formula (1): (in the formula (1), R1 represents an alkyl group having 1 to 4 carbon atoms, R2 and R3 each independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group, and when R1 and R2 are alkyl groups, R1 and R2 may be bonded to each other to form a ring structure).
H2O2-oxidation of alcohols promoted by polymeric phosphotungstate catalysts
Yamada, Yoichi M.A.,Jin, Chung Keun,Uozumi, Yasuhiro
supporting information; experimental part, p. 4540 - 4543 (2010/12/25)
A novel polymeric phosphotungstate catalyst bearing a poly(ethylene oxide-pyridinium) matrix was developed that efficiently promoted oxidation of a variety of alcohols, including highly sterically demanding neopentyl alcohols, with hydrogen peroxide, to afford the corresponding carbonyl compounds in up to quantitative yield. The chemoselective oxidation of sterically hindered secondary alcohols in the presence of primary alcohols was achieved. The catalyst could be reused four times without any loss of catalytic activity.
