1029272-42-1Relevant articles and documents
Transfer hydrogenation of cyclic carbonates and polycarbonate to methanol and diols by iron pincer catalysts
Liu, Xin,De Vries, Johannes G.,Werner, Thomas
, p. 5248 - 5255 (2019)
Herein, we report the first example on the use of an earth-abundant metal complex as the catalyst for the transfer hydrogenation of cyclic carbonates to methanol and diols. The advantage of this method is the use of isopropanol as the hydrogen source, thus avoiding the handling of flammable hydrogen under high pressure. The reaction offers an indirect route for the reduction of CO2 to methanol. In addition, poly(propylene carbonate) was converted to methanol and propylene glycol. This methodology can be considered as an attractive opportunity for the chemical recycling of polycarbonates.
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Ward et al.
, p. 541,542 (1944)
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Synthesis of α-hydroxy ketones and vicinal (R, R)-diols by Bacillus clausii DSM 8716T butanediol dehydrogenase
Bongaerts, Johannes,Jablonski, Melanie,Kipp, Carina Ronja,Molinnus, Denise,Muschallik, Lukas,Pohl, Martina,Sch?ning, Michael J.,Selmer, Thorsten,Siegert, Petra,Wagner, Torsten
, p. 12206 - 12216 (2020)
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.
Biocatalytic production of alpha-hydroxy ketones and vicinal diols by yeast and human aldo-keto reductases
Calam, Eduard,Porté, Sergio,Fernández, M. Rosario,Farrés, Jaume,Parés, Xavier,Biosca, Josep A.
, p. 195 - 203 (2013)
The α-hydroxy ketones are used as building blocks for compounds of pharmaceutical interest (such as antidepressants, HIV-protease inhibitors and antitumorals). They can be obtained by the action of enzymes or whole cells on selected substrates, such as diketones. We have studied the enantiospecificities of several fungal (AKR3C1, AKR5F and AKR5G) and human (AKR1B1 and AKR1B10) aldo-keto reductases in the production of α-hydroxy ketones and diols from vicinal diketones. The reactions have been carried out with pure enzymes and with an NADPH-regenerating system consisting of glucose-6-phosphate and glucose-6-phosphate dehydrogenase. To ascertain the regio and stereoselectivity of the reduction reactions catalyzed by the AKRs, we have separated and characterized the reaction products by means of a gas chromatograph equipped with a chiral column and coupled to a mass spectrometer as a detector. According to the regioselectivity and stereoselectivity, the AKRs studied can be divided in two groups: one of them showed preference for the reduction of the proximal keto group, resulting in the S-enantiomer of the corresponding α-hydroxy ketones. The other group favored the reduction of the distal keto group and yielded the corresponding R-enantiomer. Three of the AKRs used (AKR1B1, AKR1B10 and AKR3C1) could produce 2,3-butanediol from acetoin. We have explored the structure/function relationships in the reactivity between several yeast and human AKRs and various diketones and acetoin. In addition, we have demonstrated the utility of these AKRs in the synthesis of selected α-hydroxy ketones and diols.
Reactivity of the CH-bonds of 2-butanol in liquid-phase oxidation
Puchkov,Nepomnyashchikh, Yu. V.
, p. 2337 - 2343 (2017)
The kinetics of product accumulation is studied in the azodiisobutyronitrile-initiated oxidation of 2-butanol. The relative reactivity for all types of the CH-bonds of 2-butanol is determined for reactions with peroxyl radicals at 60°C. It is established that the hydroxyl functional group of 2-butanol activates the CHbond in position 2 (α) and deactivates CH-bonds in positions 1, 3 (β), and 4 (γ), compared to the corresponding CH-bonds of saturated hydrocarbons.
Chemoenzymatic preparation of (2S,3S)- and (2R,3R)-2,3-butanediols and their esters from mixtures of d,l- and meso-diols
Liu, Rong,Hoegberg, Hans-Erik
, p. 771 - 778 (2001)
An efficient method of preparing the pure enantiomers of 2,3-butanediol from commercially available mixtures of the d,l- and meso-isomers was developed. It furnished (2S,3S)-2,3-butanediol with >99% e.e. and a >99.5/0.5 diastereomeric ratio and (2R,3R)-2,3-butanediol in 95% e.e. and >95/5 diastereomeric ratio.
Asymmetric Hydrosilylation of Symmetrical Diketones Catalyzed by a Rhodium Complex with Trans-Chelating Chiral Diphosphine EtTRAP
Kuwano, Ryoichi,Sawamura, Masaya,Shirai, Junya,Takahashi, Masatoshi,Ito, Yoshihiko
, p. 5239 - 5242 (1995)
Asymmetric hydrosilylation of symmetrical diketones with diphenylsilane in the presence of catalytic amount (/ = 100> of rhodium complex coordinated with trans-chelating chiral phosphine ligand EtTRAP gave corresponding optically active symmetrical diols with high enantiomeric excesses.
