Highly Efficient Asymmetric Transcyanation of Acetyltrimethylsilane with Acetone Cyanohydrin Catalyzed by (R)-Oxynitrilase from Prunus Japonica Seed Meal  

郁李仁（R）-醇腈酶高效催化乙酰基三甲基硅烷与丙酮氰醇不对称转氰

作　　者：黄舜荣 吴虹 宗敏华 

机构地区：[1]South China University of Technology

出　　处：《Chinese Journal of Chemical Engineering》2005年第5期663-668,共6页中国化学工程学报（英文版）

基　　金：国家自然科学基金，国家自然科学基金

摘　　要：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 34.5g·L^-1 and 14mmol· L^-1, 28mmol· 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.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 13% (by volume), 5.0 and 30℃, respectively, while the initial reaction rate, the substrate conversion and the product enantiomeric excess were 1.34mmol. 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.

关 键 词：asymmetric transcyanation acetyltrimethylsilane （R）-oxynitrilase （R）-2-trimethylsilyl-2-hydroxylpropionitrile 

分 类 号：O627.41[理学—有机化学] O623.76[理学—化学]