手性食品香料3-羟基-5-甲基-2-己酮及3-羟基-2-戊酮的制备  

Preparation of Chiral Flavors 3-Hydroxy-5-methyl-2-hexanone and 3-Hydroxy-2-pentanone

作　　者：刘永国[1,2] 孙宝国[2] 田红玉[2] 

机构地区：[1]陕西科技大学化学与化工学院,西安710021 [2]北京工商大学食品学院北京市食品风味化学重点实验室,北京100048

出　　处：《中国食品学报》2013年第3期42-46,共5页Journal of Chinese Institute Of Food Science and Technology

基　　金：国家自然科学基金项目(31071610);“十二五”国家科技支撑计划项目(2011BAD23B01);北京市教育委员会科技发展计划重点项目(KZ201110011015);北京市属高等学校人才强教计划资助项目(PHR201008244,PHR20090504)

摘　　要：分别以5-甲基-2-己酮和2-戊酮为原料,通过烯醇硅醚的中间体,利用Sharpless不对称双羟基化反应,制备3-羟基-5-甲基-2-己酮和3-羟基-2-戊酮的各种立体异构体。5-甲基-2-己酮在六甲基二硅胺的作用下,与三甲基碘硅烷反应得到热力学稳定的烯醇硅醚1,4-二甲基-1-戊烯基三甲基硅醚,产率达78.0%;然后进行Sharpless不对称双羟基化反应。用AD-mix-α氧化得到(S)-3-羟基-5-甲基-2-己酮,产率71.8%,对映体过量(ee)值68.6%;用AD-mix-β氧化得到(R)-3-羟基-5-甲基-2-己酮,产率76.9%,ee值77.2%。2-戊酮,通过同样的方法转化得到(S)-3-羟基-2-戊酮(产率65.4%,ee值77.2%)和(R)-3-羟基-2-戊酮(产率71.9%,ee值84.9%)。The two stereoisomers of 3-hydroxy-5-methyl-2-hexanone and 3-hydroxy-2-pentanone were prepared by Sharpless dihydroxylation of silyl enol ethers as intermediates starting from 5-methyl-2-hexanone and 2-pentanone respec- tively. 5-Methyl-2-hexanone reacted with Me3SiI under the presence of hexamethyldisilazane to give a thermally stable silyl enol ether 1,4-dimethyl-l-pentenyl trimethylsilyl ether in 78.0% yield. The obtained silyl enol ether was oxidized through Sharpless asymmetric dihydroxylation using AD-mix-α to give （S）-3-hydroxy-5-methyl-2-hexanone in 71.8% yield with 68.6% ee; while AD-mix-β gave （R）-3-hydroxy-5-methyl-2-hexanone in 76.9% yield with 77.2% ee. And 2-pentanone was transformed through the same way to （S）-3-hydroxy-2-pentanone（yield 65.4% and 77.2% ee） and （R）- 3-hydroxy-2-pentanone （yield 71.9% and 84.9% ee）.

关 键 词：3-羟基-5-甲基-2-己酮 3-羟基-2-戊酮 Sharpless不对称双羟基化反应 手性偶姻食品香料 

分 类 号：TS264.3[轻工技术与工程—发酵工程]