Electrocatalytic oxidation of alcohols by a carbon-supported Rh porphyrin

A Rh porphyrin on carbon black was shown to catalyze the electro-oxidation of several aliphatic alcohols (ethanol, 1-propanol, and 2-propanol) and benzyl alcohols. The overpotentials for alcohol oxidation were very low. The reaction mechanism and substrate specificity are discussed.     

Microbial oxidation of α-allenic alcohols

By microbial oxidation of α-allenic alcohols, α-allenic acids are formed.     

Ruthenium-catalysed oxidation of alcohols to amides using a hydrogen acceptor

A wider investigation into the synthesis of secondary amides from primary alcohols using a hydrogen acceptor using commercially available [Ru(p-cymene)Cl₂]₂ with bis(diphenylphosphino)butane (dppb) as the catalyst. The report looks at over 50 examples with varying functionality and steric bulk, whilst also covering the first reported results using microwave heating to effect the transformation.     

Aerobic oxidation of alcohols using bismuth bromide as a catalyst

We developed an environmentally friendly method for aerobic oxidation of alcohols using a commercially available, relatively benign bismuth salt as a catalyst. We found that the catalytic combination of BiBr₃ with nitric acid is key for enhancing the reactivity. The reaction proceeds well under air, making the use of pure oxygen unnecessary. Each of the primary or secondary alcohols tested was oxidized to the corresponding aldehydes or ketones using this protocol.     

Aerobic oxidation of primary alcohols in the presence of activated secondary alcohols

Chemoselective aerobic oxidation of primary alcohols in the presence of activated secondary alcohols was effected under irradiation of visible light by using (nitrosyl)Ru(salen) complex 6 that possesses bulky 1-ethyl-1-methylpropyl groups at C3, C3′, C5 and C5′, as catalyst. For example, oxidation of n-decanol was >50 times faster than oxidation of 1-phenylethanol at 10 °C.     

由长链醇选择性氧化制备香料(英文)

The activity and the selectivity of Ru and Pt based carbon catalysts in the selective oxidation of long-chain aliphatic alcohols (C8, C10, C12) have been investigated. Ru/AC and Pt/AC always showed good initial activity, however deactivation phenomena rapidly depressed the catalytic per-formance of the catalysts. These phenomena can be limited by modification of Ru/AC and Pt/AC with Au improving the durability of the catalyst. Ru/AC and AuRu/AC showed good selectivity to the corresponding aldehyde (95%) making these catalysts promising for fragrances manufacturing. The advantage in using Au modified catalyst lies on the easier regeneration procedure com-pared to the one necessary for Ru/AC. Pt /AC and AuPt/AC showed a lower selectivity to aldehyde promoting the formation of the acid and the ester formation respectively. The addition of water in the solvent system speeds up the reaction rate but drastically decreased the selectivity to aldehyde especially in the case of Pt based catalysts.     

Lewis acid-activated oxidation of alcohols by permanganate

The oxidation of alcohols by KMnO(4) is greatly accelerated by various Lewis acids. Notably the rate is increased by 4 orders of magnitude in the presence of Ca(2+). The mechanisms of the oxidation of CH(3)OH and PhCH(OH)CH(3) by MnO(4)(-) and BF(3)·MnO(4)(-) have also been studied computationally by the DFT method.     

Selective photocatalytic oxidation of alcohols by heteropolytungstates

A series of primary, secondary, saturated and unsaturated alcohols have been selectively oxidized photocatalytically to the corresponding aldehydes and ketones by a series of heteropolytungstates using near visible and UV light. Stoichiometrically, one photon adds two electrons onto the heteropolytungstates and produces one molecule of aldehyde or ketone. Using oxygen-saturated solutions, the photocatalytic cycle is obtained at the early stage of the photoredox reaction, with optimization of the quantum yield for the oxidized organic product being ∼ 0.1. After at least 20 photocatalytic cycles, when the production of the organic oxidation product was 20 times the amount of catalyst, there was no sign of decomposition of the catalyst.     

Ruthenium-catalyzed oxidation of alcohols with sodium bromate

Ruthenium trichloride-catalyzed oxidation of secondary alcohols with sodium bromate under basic conditions affords ketones in the excellent yields.     

Microwave-assisted oxidation of alcohols using Magtrieve™

Primary and secondary alcohols can be selectively oxidized under microwave irradiation into the corresponding aldehydes and ketones within 5-30 min using commercially available and magnetically retrievable Magtrieve™.     

Oxovanadium complex-catalyzed aerobic oxidation of propargylic alcohols

A catalytic system consisting of vanadium oxyacetylacetonate [VO(acac)(2)] and 3 A molecular sieves (MS3A) in acetonitrile works effectively for the aerobic oxidation of propargylic alcohols [R(1)CH(OH)Ctbd1;CR(2)] to the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Although the reactivity of alpha-acetylenic alkanols (R(1) = alkyl) is lower compared to that of the alcohols of R(1) = aryl, alkenyl, and alkynyl, the use of VO(hfac)(2) as a catalyst and the addition of hexafluoroacetylacetone improve the product yield in these cases. A catalytic cycle involving a vanadium(V) alcoholate species and beta-hydrogen elimination from it has been proposed for this oxidation.     

Enantioselective oxidation of secondary alcohols at a quinohaemoprotein alcohol dehydrogenase electrode

Quinohaemoprotein alcohol dehydrogenase fromComamonas testosteroni was co-immobilized with a redox polymer (a poly(vinylpyridine) complex functionalized with osmium bis(bipyridine) chloride) on an electrode. The enzyme electrode readily oxidizes primary alcohols and secondary alcohols with maximum current densities varying between 0.43 and 0.98 A m^-2 depending on the substrate and the operation temperature. The affinity of the enzyme for aliphatic alcohols increases with the chain length of the substrate (i.e., 1-pentano1 [K_m = 0.006 mM] is a much better substrate than ethanol [K_m= 2.2 mM]). The same property is observed for secondary alcohols in the series 2-propanol (K_m = 22 mM) to 2-octano1 (K_m = 0.05 mM). The enzyme electrode is enantioselective in the oxidation of secondary alcohols. A strong preference is observed for the S-2-alcohols; the enantioselectivity increases with increasing chain length. The enantiomeric ratio (E) increases from 13 for (R,S)-2-butanol to approximately 80 for (R,S)-2-heptanol and (R,S)-2-octanol. This makes the enzyme electrode, potentially, a powerful tool for the preparation of a large range of alkanones and/or for the (kinetic) resolution of racemic alcohols.     

Na-promoted aerobic oxidation of alcohols to ketones

Aerobic oxidation of a number of diaryl and arylalkyl carbinols to ketones was promoted by Na in THF at room temperature with up to 99% yield. This new oxidation method is also selective with good efficiency for the oxidation of benzylic secondary alcohols but not for a primary alcohol or nonbenzylic secondary alcohols. Under nitrogen, a catalytic amount of Ni or transition metal halides such as CoCl₃, FeCl₃, and NiCl₃ in combination with Na was also found to conduct a dehydrogenation of a secondary alcohol to the corresponding ketone in high yield at room temperature.     

The aerobic oxidation of alcohols with a ruthenium porphyrin catalyst in organic and fluorinated solvents

Carbonylruthenium tetrakis(pentafluorophenyl)porphyrin Ru(TPFPP)(CO) was utilized for the aerobic oxidation of alcohols. The in situ activation of the catalyst with mCPBA provided a species capable of catalyzing the oxidation of alcohols with molecular oxygen. The choice of solvent and additive was crucial to obtaining high activity and selectivity. Secondary aromatic alcohols were oxidized in the presence of the ruthenium porphyrin and tetrabutyl ammonium hydroxide in the solvent bromotrichloromethane, enabling high yields to be achieved (up to 99%). Alternatively, alcohols could be oxidized in perfluoro(methyldecalin) with the ruthenium porphyrin at higher temperatures (140 degrees C) and elevated oxygen pressures (50 psi).     

The conversion of primary alcohols to the corresponding aldehydes by a modified lead tetraacetate oxidation

A novel metod for obtaining aldehydes in good yield from primary alcohols has been devised, using the combination lead tetraacetate—manganous diacetate as the oxidizing agent.