环糊精介入酵母细胞催化芳香酮的不对称还原反应
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摘要
本文首次系统的研究了环糊精介入酵母细胞催化芳香酮的不对称还原反应,以β-环糊精和自制的羟丙基-β-环糊精作为手性添加剂,主要考察了环糊精结构及添加量、底物芳香酮的结构和性质等对反应结果的影响(底物转化率和S-产物ee值)。主要结论如下:
1、羟丙基-β-环糊精的优化合成条件为:反应时间为24 h,反应温度为5℃,反应物环氧丙烷与β-环糊精的摩尔比为1:6,NaOH的质量浓度为3%,收率为22.5%。
2、通过正交实验确定了影响芳香酮-β-环糊精包合物包合率的主次因素:芳香酮与β-环糊精的摩尔配比起主要作用,温度次之,时间对包合率的影响最小;苯乙酮、苯丙酮与β-环糊精的包合物在包合温度为50℃,摩尔配比为1:7,时间为2 h时形成稳定的包合物,此时包合率分别为80.6%和59.1%。4’-甲基苯乙酮-β-环糊精与4’-氯苯乙酮-β-环糊精包合物在包合温度为50℃,摩尔配比为1:7,包合时间为1 h形成稳定的包合物,该条件下包合率分别为74.8%和65%。
3、研究了手性添加剂介入酵母细胞催化芳香酮的不对称还原反应,分别考察了添加剂β-环糊精和羟丙基-β-环糊精对催化芳香酮的不对称还原反应的影响,结果表明芳环上取代基的空间效应和电子效应对底物转化率和产物对映体过量值有显著的影响,苯丙酮的转化率提高了18.5%,S-(4'-氯苯基)乙醇的ee值提高了22.9%。同时研究了在添加适量β-环糊精和羟丙基-β-环糊精后,转化时间对各芳香酮反应结果的影响。由实验结果可以知,酵母细胞催化芳香酮的不对称还原反应中,不对称催化还原反应结果由底物羰基两边取代基的空间效应和电子效应共同决定,整个生物催化过程中,酵母细胞中的氧化还原酶和手性添加剂共同影响反应结果;但反应本质是由酵母细胞和底物特性决定,它们决定着添加剂对反应结果影响的程度和性质。
The asymmetric reduction of aromatic ketones catalyzed by yeast cell in the presence of cyclodextrin is systematicly studied in this paper, employingβ-cyclodextrin and self-made hydroxypropyl-β-cyclodextrin as chiral additives. The impact of the structure and addition amount of cyclodextrin, the structure and nature of aromatic ketone on the reaction results(conversion and ee) is detailed researched. Main conclusions are as follows:
1 The optimized condition for synthesis of hydroxypropyl-β-cyclodextrin was: the reaction time was 24 h, the reaction temperature was 5℃, the molar ratio of epoxypropane toβ-cyclodextrin was 1:6, and the concentration of NaOH was 3%. The yield of hydroxypropyl-β-cyclodextrin reached 22.5% under the condition.
2 Range an alysis showed the molar rate of aromatic ketones toβ-cyclodextrin was the most important factor affecting the inclusion rate of aromatic ketones-β- cyclodextrin, followed by the inclusion temperature and then the inclusion time. Acetophenone-β- cyclodextrin and propiophenone-β-cyclodextrin can form steady inclusion complex and the inclusion rate respectively was 80.6% and 59.1% under this conditions: inclusion temperature was 50℃, the molar ratio was 1:7 and the inclusion time was 2h. While for 4'-methyl- acetophenone-β-cyclodextrin and 4'-chlorophenyl-acetophenone-β-cyclodextrin, the inclusion rate reached 74.8% and 65% when inclusion temperature was 50℃, the molar ratio was 1:7 and the inclusion time was 1 h.
3 The asymmetric reduction of aromatic ketones catalyzed by yeast cell in the presence of chiral additiveβ-cyclodextrin and hydroxypropyl-β-cyclodextrin were detailed investigated by studying the influences of additiveβ-cyclodextrin and hydroxypropyl-β-cyclodextrin. The results showed that the substrate conversion rate and the product enantiomeric excess value were markedly affected by both steric effect and electronic effect of substituted group. The acetophenone conversion rate increased by 18.5 % and ee value of S-(4'-chlorobenzene) ethanol improved by 22.9%. Cyclodextrions affected the reaction results by enhancing the catalytic efficiency of yeast fermentation broth and inclusion of the substrate, among which the key factor is p-substituted group of the substrate aromatic cycle. According to the above experiments, the results of asymmetric reduction of aromatic ketones catalyzed by yeast cells were determined by both the space and electronic effects which join the carbonyl. In the whole biocatalysis process, oxidoreductase in yeast cells and chiral additives affect the reaction results together, however, the essence of reaction were determined by yeast cells and substrate characteristics, which determined the effect of additives on the extent and nature of the reaction.
1、羟丙基-β-环糊精的优化合成条件为:反应时间为24 h,反应温度为5℃,反应物环氧丙烷与β-环糊精的摩尔比为1:6,NaOH的质量浓度为3%,收率为22.5%。
2、通过正交实验确定了影响芳香酮-β-环糊精包合物包合率的主次因素:芳香酮与β-环糊精的摩尔配比起主要作用,温度次之,时间对包合率的影响最小;苯乙酮、苯丙酮与β-环糊精的包合物在包合温度为50℃,摩尔配比为1:7,时间为2 h时形成稳定的包合物,此时包合率分别为80.6%和59.1%。4’-甲基苯乙酮-β-环糊精与4’-氯苯乙酮-β-环糊精包合物在包合温度为50℃,摩尔配比为1:7,包合时间为1 h形成稳定的包合物,该条件下包合率分别为74.8%和65%。
3、研究了手性添加剂介入酵母细胞催化芳香酮的不对称还原反应,分别考察了添加剂β-环糊精和羟丙基-β-环糊精对催化芳香酮的不对称还原反应的影响,结果表明芳环上取代基的空间效应和电子效应对底物转化率和产物对映体过量值有显著的影响,苯丙酮的转化率提高了18.5%,S-(4'-氯苯基)乙醇的ee值提高了22.9%。同时研究了在添加适量β-环糊精和羟丙基-β-环糊精后,转化时间对各芳香酮反应结果的影响。由实验结果可以知,酵母细胞催化芳香酮的不对称还原反应中,不对称催化还原反应结果由底物羰基两边取代基的空间效应和电子效应共同决定,整个生物催化过程中,酵母细胞中的氧化还原酶和手性添加剂共同影响反应结果;但反应本质是由酵母细胞和底物特性决定,它们决定着添加剂对反应结果影响的程度和性质。
The asymmetric reduction of aromatic ketones catalyzed by yeast cell in the presence of cyclodextrin is systematicly studied in this paper, employingβ-cyclodextrin and self-made hydroxypropyl-β-cyclodextrin as chiral additives. The impact of the structure and addition amount of cyclodextrin, the structure and nature of aromatic ketone on the reaction results(conversion and ee) is detailed researched. Main conclusions are as follows:
1 The optimized condition for synthesis of hydroxypropyl-β-cyclodextrin was: the reaction time was 24 h, the reaction temperature was 5℃, the molar ratio of epoxypropane toβ-cyclodextrin was 1:6, and the concentration of NaOH was 3%. The yield of hydroxypropyl-β-cyclodextrin reached 22.5% under the condition.
2 Range an alysis showed the molar rate of aromatic ketones toβ-cyclodextrin was the most important factor affecting the inclusion rate of aromatic ketones-β- cyclodextrin, followed by the inclusion temperature and then the inclusion time. Acetophenone-β- cyclodextrin and propiophenone-β-cyclodextrin can form steady inclusion complex and the inclusion rate respectively was 80.6% and 59.1% under this conditions: inclusion temperature was 50℃, the molar ratio was 1:7 and the inclusion time was 2h. While for 4'-methyl- acetophenone-β-cyclodextrin and 4'-chlorophenyl-acetophenone-β-cyclodextrin, the inclusion rate reached 74.8% and 65% when inclusion temperature was 50℃, the molar ratio was 1:7 and the inclusion time was 1 h.
3 The asymmetric reduction of aromatic ketones catalyzed by yeast cell in the presence of chiral additiveβ-cyclodextrin and hydroxypropyl-β-cyclodextrin were detailed investigated by studying the influences of additiveβ-cyclodextrin and hydroxypropyl-β-cyclodextrin. The results showed that the substrate conversion rate and the product enantiomeric excess value were markedly affected by both steric effect and electronic effect of substituted group. The acetophenone conversion rate increased by 18.5 % and ee value of S-(4'-chlorobenzene) ethanol improved by 22.9%. Cyclodextrions affected the reaction results by enhancing the catalytic efficiency of yeast fermentation broth and inclusion of the substrate, among which the key factor is p-substituted group of the substrate aromatic cycle. According to the above experiments, the results of asymmetric reduction of aromatic ketones catalyzed by yeast cells were determined by both the space and electronic effects which join the carbonyl. In the whole biocatalysis process, oxidoreductase in yeast cells and chiral additives affect the reaction results together, however, the essence of reaction were determined by yeast cells and substrate characteristics, which determined the effect of additives on the extent and nature of the reaction.
引文
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