Asymmetric synthesis of (-)-1-trimethylsilyl-ethanol with immobilized Saccharomyces cerevisiae cells in water/organic solvent biphasic system was studied. The effects of shake speed, hydrophobicity of organic solvent, volume ratio of water phase to organic phase, pH value of aqueous phase and reaction temperature on the initial reaction rate, maximum yield and enantiomeric excess (ee) of the product were systematically explored. All the above-mentioned factors had significant influence on the reaction. n-Hexane was found to be the best organic solvent for the reaction. The optimum shake speed, volume ratio of water phase to organic phase, pH value and reaction temperature were 150 r.min-1, 1/2, 8 and 30 ℃ respectively, under which the maximum yield and enantiomeric excess of the product were as high as 96.8% and 95.7%, which are 15% and 16% higher than those of the corresponding reaction performed in aqueous phase. To our best knowledge, this is the most satisfactory result obtained. 相似文献
Highly efficient asymmetric transcyanation of acetyltrimethylsilane with acetone cyanohydrin in an aqueous/organic biphasic system catalyzed with(R)-oxynitrilase from defatted Prunus Japonica seed meal for the preparation of optically active(R)-2-trimethylsilyl-2-hydroxyl-propionitrile was successfully carried out for the first time.For better understanding of the reaction,various influential variables were examined with respect to the initial reaction rate,the substrate conversion and the product enantiomeric excess(e.e.).Diisopropyl ether was found to be the best organic phase for this reaction among all the organic solvents tested.The optimal concentrations of Prunus Japonica seed meal powder,acetyltrimethylsilane and acetone cyanohydrin,volume ratio of aqueous phase to organic phase,buffer pH value and the reaction temperature were 34. 5 g.L~(-1) and 14 mmol·L~(-1) ,28 mmol.L~(-1) , 13%(by volume),5. 0 and 30℃,respectively,while the initial reaction rate,the substrate conversion and the product enantiomeric excess were 1. 34 mmol.L~(-1) .h~(-1) ,99. 0% and 99. 0%,respectively.The comparative study demonstrated that silicon atom in substrate showed great effect on the reaction and acetyltrimethylsilane was a much better substrate for(R)-hydroxynitrile lyase from Prunus Japonica seed than its carbon analogue 3,3-dimethyl-2-butanone. 相似文献
Starting from an adequate ketone precursor previous reports required three steps for the preparation of (R)‐2,3,4,9‐tetrahydro‐1H‐carbazol‐3‐amine, a key intermediate for the synthesis of the antiallergic drug ramatroban. A single biocatalytic step was sufficient to prepare the target amine with >97% ee (HPLC) via reductive amination of the corresponding ketone using an ω‐transaminase as biocatalyst. Since the ketone was barely soluble under the reaction conditions employed, it was provided as a solid and still the reaction went to completion within 4 h at 50 mM substrate concentration. Although 2‐propylamine is regarded as an ideal amine donor, it turned out to be detrimental for the specific ketone precursor leading to the formation of various side products. These could be avoided by using (R)‐1‐phenylethylamine as the best suited amine donor. An alternative work‐up was developed via freeze‐drying of the reaction mixture, enabling the isolation of the desired (R)‐amine in excellent yield (96%) and enantiopure form on a preparative scale (500 mg). No purification steps (e.g., column chromatography, crystallisation) were required.
Asymmetric synthesis of (-)-1-trimethylsilyl-ethanol with immobilized Saccharomyces cerevisiae cells in water/organic solvent biphasic system was studied,The effects of shake speed,hydrophobictiy of organic solvent ,volume ratio of water phase to organic phase,pH value of aqueous phase and reaction temperature on the initial reaction rate,maximum yield and enantiomeric excess(ee) of the product were systematically explored,All the above-mentioned factors had significant infuence on the reaction.n-Hexane was found to be the best organic solvent for the reaction.The optimum shake speed,volume ratio of water phase to organic phase,pH value and reaction temperature were 150 r.min^-1,1/2,8 and 30℃ respectively,under which the maximum yield and enantiomeric excess of the product were as high as 96.8% and 95.7%,which are 15% and 16% higher than those of the corresponding reaction performed in aqueous phase ,To our best knowledge,this is the most satisfactory result obtained. 相似文献
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