手性苄基甲基亚砜的氯过氧化物酶催化定向合成

doi:10.6023/A1106212

化学学报 ›› 2012, Vol. 0 ›› Issue (04): 465-470.DOI: 10.6023/A1106212 上一篇下一篇

研究论文

手性苄基甲基亚砜的氯过氧化物酶催化定向合成

汪丽敏^a, 吴金跃^a, 蒋育澄^a,b, 胡满成^a,b, 李淑妮^a,b, 翟全国^a,b

a 陕西师范大学化学化工学院西安 710062;
b 陕西师范大学大分子科学陕西省重点实验室西安 710062

投稿日期:2011-06-21 修回日期:2011-09-02 发布日期:2011-10-20
通讯作者: 蒋育澄
基金资助:
国家自然科学基金(No. 20876094)及中央高校基本科研业务费专项资金(No. GK201001005)资助.

Asymmetry Synthesis of Chiral Sulfoxide Catalyzed by Chloroperoxidase

Wang Limin^a, Wu Jinyue^a, Jiang Yucheng^a,b, Hu Mancheng^a,b, Li Shuni^a,b, Zhai Quanguo^a,b

a School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710062;
b Key Laboratory of Macromolecular Science of Shaanxi Province, Shaanxi Normal University, Xi'an 710062

Received:2011-06-21 Revised:2011-09-02 Published:2011-10-20
Supported by:
This work was supported by the National Natural Science Foundation of China (No. 20876094) and the Fundamental Research Funds for the Central Universities (No. GK201001005).

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摘要/Abstract

基于氯过氧化物酶(CPO)对有机底物的手性识别功能, 以CPO 催化、叔丁基过氧化氢(TBHP)氧化甲基苄基硫醚合成手性R-苄基甲基亚砜, 并在反应体系中引入多羟基化合物及季铵盐提高了目标产物的产率; 反应主要受体系的pH 值、氧化剂类型、反应时间、氧化剂/底物摩尔比, 以及CPO用量等因素控制. 引入多羟基化合物(甘油, PEG400, PEG600) 时, R-苄基甲基亚砜的产率及ee 值可分别达到65.5%和96.3%; 而引入季铵盐(TEABr, TPABr, TBABr)时, 其产率提高到78.2%～68.5%, ee 值为95.4%～94%. UV-vis 及荧光光谱分析表明反应体系中引入少量添加剂时CPO 活性中心的血红素辅基暴露程度增加, 底物容易接近, 同时CPO 的α-螺旋结构得以加强, 从而有效改善了CPO 的催化性能. 与目前的合成方法相比, CPO 酶促氧化制备手性R-苄基甲基亚砜高效、定向, 酶用量极少, 具有一定的产业化应用潜能.

关键词: 氯过氧化物酶, 手性苄基甲基亚砜, 定向磺化氧化, 多羟基化合物, 季铵盐

Benzyl alkyl sulfide was turned into chiral R-sulfoxide using chloroperoxidase (CPO)-catalyzed oxidation of (TBHP) based on CPO’s chiral recognization to organic substrate. The yield of aim products was enhanced by the introduction of polyhydroxy compound and quaternary ammonium salt. The reaction was mainly controlled by factors such as pH, oxidants, reaction time, molar ratio of oxidant/substrate, and CPO consumption. The sulfoxide yield and enantiomeric excess (ee) reached 65.5% and 96.3% when polyhydroxy compounds (glycerol, PEG400 or PEG600) were introduced into reaction system. The yield and ee of 78.2%～68.5% and 95.4%～94% were obtained when quaternary ammonium salt (TEABr, TPABr or TBABr) was introduced. UV-vis and fluorescence spectrum assay indicated that it was easier for CPO to bind with the substrate because the introduction of above additives would intensify the exposure of heme. Moreover, it was also favorable for CPO catalytic performance due to the improvement of α-helix structure of CPO. Compared to those reported methods, the preparation of chiral sulfoxide catalyzed by CPO was very efficient. CPO consumption was very small which would ensure its potential application in industry.

Key words: chloroperoxidase, chiral sulfoxide, enantio-sulfoxidation, polyhydroxy compound, quaternary ammonium salt

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汪丽敏, 吴金跃, 蒋育澄, 胡满成, 李淑妮, 翟全国. 手性苄基甲基亚砜的氯过氧化物酶催化定向合成[J]. 化学学报, 2012, 0(04): 465-470.

Wang Limin, Wu Jinyue, Jiang Yucheng, Hu Mancheng, Li Shuni, Zhai Quanguo. Asymmetry Synthesis of Chiral Sulfoxide Catalyzed by Chloroperoxidase[J]. Acta Chimica Sinica, 2012, 0(04): 465-470.

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手性苄基甲基亚砜的氯过氧化物酶催化定向合成

Asymmetry Synthesis of Chiral Sulfoxide Catalyzed by Chloroperoxidase

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