水/有机溶剂双相中郁李醇腈酶催化含硅(R)-酮氰醇对映选择性合成  

Enantioselective Synthesis of Silicon-Containing (R)-Ketone Cyanhydrin Catalyzed by (R)-Oxynitrilase from Plum in an Aqueous/Organic Biphasic System

作　　者：刘森林[1] 宗敏华[2] 

机构地区：[1]深圳大学生命科学学院,广东深圳518060 [2]华南理工大学生物工程系,广东广州510640

出　　处：《催化学报》2006年第1期25-28,共4页

基　　金：国家自然科学基金(20376026);高等学校博士学科点专项科研基金(20030561017);教育部科技项目(104147);深圳市科技计划项目(200325)资助.

摘　　要：研究了水/有机溶剂双相中来源于郁李仁的(R)醇腈酶催化2三甲基硅2乙酮与2甲基2羟基丙腈对映选择性合成(R)2三甲基硅2羟基丙腈,初步探讨了反应时间、酶粉颗粒大小、底物浓度、底物配比和酶添加量对转氰反应的影响.结果表明,适宜的反应条件为:反应时间96h左右,酶粉颗粒大小0.3～0.45mm,底物2三甲基硅2乙酮浓度14mmol/L,底物2甲基2羟基丙腈与2三甲基硅2乙酮摩尔比2∶1,单位体积反应介质中的酶添加量43.5g/L左右.在该优化反应条件下,反应平衡转化率和产物的光学纯度(ee值)均可高达99%.对比研究发现,郁李醇腈酶催化2三甲基硅2乙酮反应在酶促反应初速率、底物转化率和产物光学纯度等方面均显著优于其碳结构类似物3,3二甲基2丁酮.The synthesis of an optically active organosilicon compound, （ R ）-2-trimethylsilyl-2-hydroxyl-ethylcyanide, through enantioselective transcyanation of acetyltrimethylsilane with acetone cyanohydrin catalyzed by （R）-oxynitrilase from defatted plum seeds in an aqueous/organic biphasic system was carried out. The conversion of acetyltrimethylsilane and enantiomeric excess of （R）-2-trimethylsilyl-2-hydroxyl-ethylcyanide were determined by gas chromatography on a β-dyelodextrin chiral column. The influences of reaction time, particle size of the crude enzyme, substrate concentration, molar ratio of two substrates, and enzyme amount on the reaction were investigated. Under the optimum conditions such as reaction time of 96 h, particle diameter of the crude enzyme of 0.3- 0.45 mm, acetyhrimethylsilane concentration of 14 mmol/L, acetone cyanohydrin to acetyhrimethylsilane molar ratio of 2 ： 1, and enzyme amount of 43.5 g/L, both acetyltrimethylsilane conversion and enantiomeric excess of the product are as high as 99%. A comparative study shows that acetyltrimethylsilane is a much better suhstrate for the （ R ）-oxynitrilase than its carbon counterpart 3, 3- dimethyl-2-butanone with respect to the reaction rate, substrate conversion, and product enantiomeric excess.

关 键 词：郁李仁 (R)-醇腈酶 2-三甲基硅-2-乙酮 氰基转移 对映选择性合成 (R)-2-三甲基硅-2-羟基丙腈 (R)-酮氰醇 有机硅 

分 类 号：O643.32[理学—物理化学]