113919-08-7

Upstream product

• 591-95-7 penta-1,2-diene 
• 5704-20-1 2-hydroxy-3-pentanone 
• 875225-67-5 4-methoxy-4-methyl-octane-3,5-diol 
• 600-18-0 2-Oxobutyric acid 
• 75-07-0 acetaldehyde 
• 123-38-6 propionaldehyde 
• 127-17-3 2-oxo-propionic acid 
• 546-67-8 lead(IV) tetraacetate 
• 71-43-2 benzene 
• 103205-82-9 2,3-dihydroxy-2-methyl-valeraldehyde 
• 4187-86-4 pent-1-yn-3-ol 
• 5551-19-9 3-ethyl-2-formyloxy-2-methyl-oxirane 
• 18218-93-4 2-methoxyacrolein 
• 925-90-6 ethylmagnesium bromide 

Downstream Products

• 3896-13-7 pentane-2,3-dione-bis-phenylhydrazone 
• 1455438-47-7 3-(4-methoxyphenylamino)pentan-2-one 

Relevant academic research and scientific papers

Enantiogenic synthesis of (R)-(-)-3-hydroxy-1-penten-4-one

Condensation of pyruvate and acrolein with whole cells of baker's yeast resulted in a mixture of 3-hydroxy-1-penten-4-one 1 and 4-hydroxy-1-penten-3-one 2. The absolute configuration (R) and the enantiomeric excess (ee 72%) of the compound 1 were determined.

Baker's Yeast Reduction of 1,2-Diketones. Preparation of Pure (S)-(-)-2-Hydroxy-1-phenyl-1-propanone

1,2-Diketones are readily reduced by fermenting baker's yeast but the reactions proceed with little selectivity.One notable exception is the reduction of 1-phenyl-1,2-propanedione which affords pure (S)-(-)-2-hydroxy-1-phenyl-1-propanone in good yield.

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and L- and D-proline respectively, in several reaction media.

Selective Hydrogenation of Diketones on Supported Transition Metal Catalysts

Abstract: The hydrogenation of α-diketones yields α-hydroxyketones or vic-diols, both compounds of great interest in fine chemistry. The reaction tests were the liquid phase hydrogenation of 2,3-butanedione and 2,3-pentanedione at mild conditions. The objectives of this work were evaluating the effect over the activity and selectivity of: (a) different transition metallic phase based catalysts supported on activated carbon, (b) the symmetry of the reactants and (c) solvents. The physicochemical characterization of the catalysts was carried out by ICP, XRD, TEM, N2 adsorption and XPS. The keto-enol equilibrium of diketones was studied by 1H-NMR. All the catalysts were active in both reactions. In terms of activity, Pt and Rh were the best active phases. For both reactants the highest selectivity towards hydroxyketones were achieved with Pd, while Ru was the most selective towards the diol. Both the activity and selectivity followed similar patterns in the hydrogenation of both diketones. The greater activity of Pt was attributed to the high dispersion of the active metal phase in this catalyst and the high efficiency of Pt for C = O bond reduction. The high selectivity of the Pd catalysts towards the intermediate product was attributed to many effects: (i) a lower interaction of the hydroxyketone with the active site as compared to the diketone, (ii) the easy reducibility of the C = C double bond on Pd, provided by the keto-enol tautomerism of diketones.

ACTION DE L'OZONE SUR DES DERIVES VINYLIQUES; REACTIONS CONSERVANT L'ENCHAINEMENT CARBONE.

Ozone reacts with vinyl derivatives (sulphides, enamines, ethers) and gives abnormal reactions or/and double bond cleavages.

Adducts of thianthrene- and phenoxathiin cation radical tetrafluoroborates to 1-alkynes. Structures and formation of 1-(5-thianthreniumyl)- and 1-(10-phenoxathiiniumyl)alkynes on alumina leading to α-ketoylides and α-ketols

Thianthrene cation radical tetrafluoroborate (Th.+BF 4-) added to the terminal alkynes 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, and 1-decyne to form trans-1,2-bis(5- thianthreniumyl)-alkene tetrafluoroborates (1-6). Similarly, addition of phenoxathiin cation radical tetrafluoroborate (PO.+BF 4-) to the same alkynes gave 1,2-bis(10-phenoxathiiniumyl) alkene tetrafluoroborates (7-12). The trans configuration of two of the adducts (1 and 4) was shown with X-ray crystallography. When solutions of 1-6 in chloroform were stirred with activated alumina, cis elimination of a proton and thianthrene (Th) occurred with the formation of 1-(5-thianthreniumyl)alkyne tetrafluoroborates (1a-6a). Similar treatment of 8-12 caused elimination of a proton and phenoxathiin (PO) with formation of 1-(10-phenoxathiiniumyl)alkene tetrafluoroborates (8a-12a). Stirring of 1a-6a with alumina for short periods of time caused their conversion into 5-[(α-keto)alkyl]thianthrenium ylides (1b-6b) and α-ketols, RC(O)CH2OH (1c-6c).

Absolute Configuration of the Product of the Acetolactate Synthase Reaction by a Novel Method of Analysis using Acetolactate Decarboxylase

Pyruvate and 2-oxobutanoate were incubated with acetolactate synthase in the presence of acetolactate decarboxylase .The exclusive production of 3-hydroxypentan-2-one showed that the α-acetohydroxybutyrate (2-ethyl-2-hydroxy-3-oxobutanoate) produced by acetolactate synthase had the (S)-configuration.The ability of acetolactate decarboxylase to catalyse rearrangement of the (R)-enantiomer of substrates via carboxylate migration was investigated using -α-acetolactate, in which the degeneracy of the rearrangement of the normal substrate was broken by isotopic labelling.The predicted sequential formation of - and -acetoin was observed.

Biotransformations with Acetolactate Decarboxylase: Unusal Conversions of Both Substrate Enantiomers into Products of High Optical Purity

Acetolactate decarboxylase catalyses the decarboxylation of both enantiomers of 2-ethyl-2-hydroxy-3-oxobutanoate to isomeric ketols of high optical purity and both enatiomers of α-acetolactate (2-hydroxy-2-methyl-3-oxobutanoate) to acetoin (3-hydroxybutan-2-one) of high optical purity.

Engineering transketolase to accept both unnatural donor and acceptor substrates and produce α-hydroxyketones

A narrow substrate range is a major limitation in exploiting enzymes more widely as catalysts in synthetic organic chemistry. For enzymes using two substrates, the simultaneous optimisation of both substrate specificities is also required for the rapid expansion of accepted substrates. Transketolase (TK) catalyses the reversible transfer of a C2-ketol unit from a donor substrate to an aldehyde acceptor and suffers the limitation of narrow substrate scope for industrial applications. Herein, TK from Escherichia?coli was engineered to accept both pyruvate, as a novel donor substrate, and unnatural acceptor aldehydes, including propanal, pentanal, hexanal and 3-formylbenzoic acid (FBA). Twenty single-mutant variants were first designed and characterised experimentally. Beneficial mutations were then recombined to construct a small library. Screening of this library identified the best variant with a 9.2-fold improvement in the yield towards pyruvate and propionaldehyde, relative to wild-type (WT). Pentanal and hexanal were used as acceptors to determine stereoselectivities of the reactions, which were found to be higher than 98% enantiomeric excess (ee) for the S configuration. Three variants were identified to be active for the reaction between pyruvate and 3-FBA. The best variant was able to convert 47% of substrate into product within 24?h, whereas no conversion was observed for WT. Docking experiments suggested a cooperation between the mutations responsible for donor and acceptor recognition, which would promote the activity towards both the acceptor and donor. The variants obtained have the potential to be used for developing catalytic pathways to a diverse range of high-value products.

Synthesis of α-hydroxy ketones and vicinal (R, R)-diols by Bacillus clausii DSM 8716T butanediol dehydrogenase

α-hydroxy ketones (HK) and 1,2-diols are important building blocks for fine chemical synthesis. Here, we describe the R-selective 2,3-butanediol dehydrogenase from B. clausii DSM 8716T (BcBDH) that belongs to the metal-dependent medium chain dehydrogenases/reductases family (MDR) and catalyzes the selective asymmetric reduction of prochiral 1,2-diketones to the corresponding HK and, in some cases, the reduction of the same to the corresponding 1,2-diols. Aliphatic diketones, like 2,3-pentanedione, 2,3-hexanedione, 5-methyl-2,3-hexanedione, 3,4-hexanedione and 2,3-heptanedione are well transformed. In addition, surprisingly alkyl phenyl dicarbonyls, like 2-hydroxy-1-phenylpropan-1-one and phenylglyoxal are accepted, whereas their derivatives with two phenyl groups are not substrates. Supplementation of Mn2+ (1 mM) increases BcBDH's activity in biotransformations. Furthermore, the biocatalytic reduction of 5-methyl-2,3-hexanedione to mainly 5-methyl-3-hydroxy-2-hexanone with only small amounts of 5-methyl-2-hydroxy-3-hexanone within an enzyme membrane reactor is demonstrated.