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Baker's Yeast Mediated Asymmetric Reduction of Ketones Having Sulfur Functional Groupes and Application to the Natural Product Synthesis

面包酵母介导的含硫官能团酮的不对称还原及其在天然产物合成中的应用

基本信息

批准号：
59470017
负责人：
FUJISAWA Tamotsu
金额：
$ 4.48万
依托单位：
Mie University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1984
资助国家：
日本
起止时间：
1984 至 1986
项目状态：
已结题

项目摘要

Introduction of sulfur functional groups to <alpha> -positions of ketones has been found to improve remarkably the substratespecificity of baker's yeast to result in high chemical and optical yields of the optically active secondary alcohols in the baker's yeast mediated asymmetric reduction of ketones. Further the reduction products have been effectively employed as useful chiral synthons for various kinds of optically active natural products by utilizing the sulfur functional groups. The reduction of 3-oxo-2-sulfenyl esters afforded optically pure (3S)-3-hydroxy-2-sulfenyl esters. 2-Substituted 3-oxo dithioesters were diastereoselectively reduced to give (2R,3S)-syn-2-substituted 3-hydroxy esters. (2R,3S)-3-Hydroxy-2-methylbutanedithioate obtained by the yeast reduction of methyl 2-methyl-3-oxobutanedithioate was converted to the pheromone of pine saw fly, (2S,3S,7S)-2-acetoxy-3, 7-dimethylpentadecane. The reduction product of 3-hydroxy-1-phenylthio-2-propanone, (S)-3-phenylthio-1,2- … More propanediol, was converted into (S)-glycidyl sulfide which was a useful chiral synthon for both R and S optically active secondary alcohols and 2-hydroxy aldehydes. The pheromone of Vespa Orientals, 5-hexadecanolide, deoxy sugars such as L-rhodinose and D-amicetose were synthesized in short steps from the glycidyl sulfide. <alpha> -(1,3-Dithian-2-yl)ketones were reduced by the yeast to afford the corresponding (S)- <alpha> -hydroxy dithianes. (S)-1-(1,3-Dithian-2-yl)-1, 4-butanediol thus obtained was effectively converted into (4S,5S)- and (4S,5R)-5-dihydroxydecan-4-olides isolated from Streptomyces griceus. The reduction of 1,2-diketones having 1,3-dithiane, phenylthio or phenylsulfonyl group at the <alpha> -position proceeds diastereoselectively to give the (S,S)-anti-1,2-diols in high enantiomeric excess. These 1,2-diol derivatives were useful chiral synthons for poly-ol natural products such as L-muscarine isolated from Amonita muscarin, (4R,5S)-5-hydroxy-2-hexen-4-olide as antifeedant for the larvae of the yellow butterfly, and L-digitoxose. The reduction of 1-(1,3-dithian-2-yl)-1,3-butanedione gave the (S,S)-1,3-diol which was converted into methyl nonactate in short steps. Further, the carbon-carbon bonds of prenyl aldehydes or alcohols possessing sulfur functional groups were reduced by the yeast to afford saturated isoprene derivatives which were useful chiral synthons for various optically active terpenoids. Less

已发现将硫官能团引入酮的α-位可显着改善面包酵母的底物特异性，从而在面包酵母介导的酮的不对称还原中产生光学活性仲醇的高化学和光学产率。此外，通过利用硫官能团，还原产物已有效地用作各种光学活性天然产物的有用手性合成子。 3-氧代-2-硫基酯的还原得到光学纯的(3S)-3-羟基-2-硫基酯。 2-取代的3-氧代二硫酯被非对映选择性还原，得到(2R,3S)-syn-2-取代的3-羟基酯。将2-甲基-3-氧代丁二硫代酸甲酯经酵母还原得到的(2R,3S)-3-羟基-2-甲基丁二硫代酯转化为松锯蝇的信息素，(2S,3S,7S)-2-乙酰氧基-3,7-二甲基十五烷。 3-羟基-1-苯硫基-2-丙酮的还原产物(S)-3-苯硫基-1,2-…更多丙二醇被转化为(S)-缩水甘油硫醚，它是R和S光学活性仲醇和2-羟基醛的有用手性合成子。由缩水甘油硫醚在短步骤中合成了胡蜂的信息素、5-十六内酯、脱氧糖（例如L-铑糖和D-酰胺糖）。 α-(1，3-二噻烷-2-基)酮被酵母还原，得到相应的(S)-α-羟基二噻烷。由此获得的(S)-1-(1，3-二噻烷-2-基)-1，4-丁二醇有效地转化为从灰色链霉菌中分离的(4S，5S)-和(4S，5R)-5-二羟基癸-4-醇。在α-位具有1，3-二噻烷、苯硫基或苯磺酰基的1，2-二酮的还原非对映选择性地进行，得到高对映体过量的(S，S)-抗1，2-二醇。这些1,2-二醇衍生物是多元醇天然产物的有用手性合成子，例如从伞菌毒蕈碱中分离出的L-毒蕈碱、作为黄蝴蝶幼虫拒食剂的(4R,5S)-5-羟基-2-己烯-4-油酯和L-洋地黄糖。 1-(1,3-二噻吩-2-基)-1,3-丁二酮的还原得到(S,S)-1,3-二醇，其在短时间内转化为九乙酸甲酯。此外，具有硫官能团的异戊二烯醛或醇的碳-碳键被酵母还原，得到饱和异戊二烯衍生物，其是各种光学活性萜类化合物的有用手性合成子。较少的