首页|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

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

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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％).
Preparation of Chiral Flavors 3-Hydroxy-5-methyl-2-hexanone and 3-Hydroxy-2-pentanone
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-methyI-2-hexanone and 2-pentanone respectively. 5-Methyl-2-hexanone reacted with Me3SiI under the presence of hexamethyldisilazane to give a thermally stable silyl enol ether 1,4- dimethyl-1 -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).

3-Hydroxy-5-methyl-2-hexanone3-hydoxy-2-pentanoneSharpless asymmetric dihydroxylationchiral acyloin flavors

刘永国、孙宝国、田红玉

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陕西科技大学化学与化工学院 西安 710021

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

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

国家自然科学基金"十二五"国家科技支撑计划项目北京市教育委员会科技发展计划重点项目北京市属高等学校人才强教计划资助项目北京市属高等学校人才强教计划资助项目

310716102011BAD23B01KZ201110011015PHR201008244PHR20090504

2013

中国食品学报
中国食品科学技术学会

中国食品学报

CSTPCDCSCD北大核心EI
影响因子：1.079
ISSN：1009-7848
年,卷(期)：2013.13(3)
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