3,5-多氧取代芪类底物的电子效应对果糖衍生手性酮催化反应的影响

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (10): 2341.

3,5-多氧取代芪类底物的电子效应对果糖衍生手性酮催化反应的影响

张成路, 邵懿, 邹立伟, 周龙, 徐德青, 高丽娜, 曲瑞峰

辽宁省生物与制药重点实验室, 辽宁师范大学化学化工学院, 大连 116029

收稿日期:2010-11-02 修回日期:2011-01-13 出版日期:2011-10-10 发布日期:2011-09-11
通讯作者: 张成路 E-mail:zhangchenglu@lnnu.edu.cn
基金资助:
辽宁省教育厅科学技术资助项目(批准号: 2009A426)和辽宁省高校创新团队资助项目(批准号: 2008T107)资助.

Influence of Electronic Effects of 3,5-Polyoxo-stilbene Substrates in the Fructose-derived Chiral Ketone System

ZHANG Cheng-Lu*, SHAO Yi, ZOU Li-Wei, ZHOU Long, XU De-Qing, GAO Li-Na, QU Rui-Feng

School of Chemistry and Chemical Engineering, Liaoning Province Key Laboratory of Biotechology and Drug Discovery, Liaoning Normal University, Dalian 116029, China

Received:2010-11-02 Revised:2011-01-13 Online:2011-10-10 Published:2011-09-11
Contact: ZHANG Cheng-Lu E-mail:zhangchenglu@lnnu.edu.cn
Supported by:
辽宁省教育厅科学技术资助项目(批准号: 2009A426)和辽宁省高校创新团队资助项目(批准号: 2008T107)资助.

摘要/Abstract

摘要： 以白藜芦醇为基本骨架设计并采用Wittig-Horner反应合成了10种芪类化合物(3a～3c, 3da, 3eaa, 3eab, 3fa, 3g～3i). 通过改变苯环上取代基的类型和位置达到了调节反式二苯乙烯共轭体系电子云分布的目的, 并在FH/3-21g水平上对相关底物进行了构型优化计算及机理推测, 探讨了底物的电子效应对催化反应选择性的影响, 并应用果糖衍生手性酮研究了芪类底物分别进行不对称环氧化反应和芳环上氧化反应的选择性. 根据研究结果确立了手性酮催化剂的应用范围, 考察了多个含氧取代基存在时对大共轭体系中反应位点的影响, 同时研究了结构与活性的关系, 分析了上述取代物的电子效应.

关键词: 1,2-二苯乙烯, 电子效应, 果糖类手性酮

Abstract: The electronic effect of catalysis and substrates plays an important role in the enantioselectivity of asymmetric catalytic reactions. The stilbenes, especially resveratrol which have a large conjugated system, have satisfactory bioactivities and can take place many reactions. Thus it is valuable to study the structure modification and structure activity relationship. Ten stilbenes were designed based on the structure of resveratrol, and synthesized through Wittig-Horner reaction in the work. The electron cloud distribution was regulated through changing the type and the position of the substances on benzene ring. The optimized configuration was obtained through calculation under FH/3-21g level. And the rational mechanism was put forward. The electronic effect of the substances on the selectivity of catalytic reaction was studied. In the system, frucase-derived chiral ketone was used to study either the asymmetric epoxidation or oxidation reaction. As a result, the applied scope of the chiral ketone was determined, the reaction position in the big conjugated system was found when polyoxo-substances exist, the rational analysis of the electronic effect of the substrates was also put forward.

Key words: Stilbene, Electronic effect, Fructose-derived chiral ketone

中图分类号:

TrendMD:

张成路邵懿邹立伟周龙徐德青高丽娜曲瑞峰. 3,5-多氧取代芪类底物的电子效应对果糖衍生手性酮催化反应的影响. 高等学校化学学报, 2011, 32(10): 2341.

ZHANG Cheng-Lu*, SHAO Yi, ZOU Li-Wei, ZHOU Long, XU De-Qing, GAO Li-Na, QU Rui-Feng. Influence of Electronic Effects of 3,5-Polyoxo-stilbene Substrates in the Fructose-derived Chiral Ketone System. Chem. J. Chinese Universities, 2011, 32(10): 2341.

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