手性香料3-巯基己醇及其乙酸酯的不对称合成  

Asymmetric syntheses of chiral flavors 3-mercapto hexanol and its acetate

作　　者：叶宏林[1] 郭安齐[2] 田红玉[1] 孙宝国[1] 欧阳天惠[1] 

机构地区：[1]北京工商大学化学与环境工程学院,北京100037 [2]河南职工医学院,河南郑州450003

出　　处：《食品工业科技》2009年第12期319-322,共4页Science and Technology of Food Industry

基　　金：国家自然科学基金资助项目(20676003);北京市属高等学校人才强教计划资助项目(PHR201008244)

摘　　要：研究了以(E)-2-己烯醛为起始原料,通过还原、Sharpless不对称环氧化、区域选择性还原、SN2亲核取代等反应制备光学活性的3-巯基己醇和3-巯基己基乙酸酯的方法。(E)-2-己烯醛通过NaBH4还原得到(E)-2-己烯醇,产率91%左右。(E)-2-己烯醇通过Sharpless不对称环氧化,得到光学活性2,3-环氧己醇,化学产率86%左右,产物e·e·值94%左右。2,3-环氧己醇用Red-Al进行区域选择性还原得到光学活性的1,3-己二醇,产率82%左右。1,3-己二醇的伯羟基转化为乙酸酯,3位羟基转化为甲磺酸酯,然后通过SN2亲核取代反应,得到3-乙酰硫基己基乙酸酯,三步反应总产率61%左右。3-乙酰硫基己基乙酸酯在氢氧化钠的作用下将乙酰硫基水解,得到3-巯基己基乙酸酯,产率85%左右;3-乙酰硫基己基乙酸酯在过量氢氧化钠的作用下完全水解,得到3-巯基己醇,产率82%左右。最终产物3-巯基己醇和3-巯基己基乙酸酯e·e·值均在94·0%左右。The syntheses of optically active 3-mercapto hexanol and 3-mercapto hexyl actetate were studied starting from （ E）- 2- hexenal through reduction, the Sharpless asymmetric epoxidation, regioseiective reduction and S,2 nucleophilic substitution.（E）-2- hexenal was reduced by NaBH4 to give （ E）-2- hexenol in about 91% yield.The optically active 2,3-epoxy hexanol was obtained through the Sharpless asymmetric epoxidation of （E）- 2-hexenol with about 94% e.e.in about 86% yield.2,3-Epoxy hexanol was regioselectively reduced with Red-AI to give optically active 1 ,3-hexanediol in about 82% yield.After the primary hydroxy group of 1 ,3-hexanediol was transformed to acetate and 3-hydroxy was transformed to mesylate,an SN2 nucleophilic substitution was carried out to form 3-acetylthio hexyl acetate.The overall yield of these three steps was about 6l %.Acetylthio group of 3-acetylthio hexyl acetate was hydrolyzed with NaOH to give 3-mercapto hexyl acetate in about 85% yield. 3-acetylthio hexyl acetate was hydrolyzed completely in the presence of excess NaOH to give 3-mercapto hexanol in about 82% yield.The final products 3- mercapto hexanol and 3- mercapto hexyl actate were obtained with about 94% e.e.

关 键 词：3-巯基己醇 3-巯基己基乙酸酯 手性香料 不对称合成 

分 类 号：TS202.3[轻工技术与工程—食品科学]