高等学校化学学报

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (3): 712.

• 研究论文 • 上一篇    下一篇

聚乙烯负载氮叶立德催化的二氢呋喃衍生物的高选择性合成

陈帅帅1,罗时忠1,李军方2,刘春荣2,孙秀丽2,唐勇2   

  1. 1. 安徽师范大学化学与材料科学学院, 安徽省功能性分子固体重点实验室, 芜湖 241000;
    2. 中国科学院上海有机化学研究所, 金属有机化学国家重点实验室, 上海 200032
  • 收稿日期:2010-10-18 修回日期:2011-01-09 出版日期:2011-03-10 发布日期:2011-02-23
  • 通讯作者: 唐勇 E-mail:tangy@mail.sioc.ac.cn
  • 基金资助:

    国家自然科学基金(批准号: 20904049)资助.

Highly Diastereroselective Synthesis of Dihydrofurans Catalyzed by PE-supported Pyridinium

CHEN Shuai-Shuai1, LUO Shi-Zhong1, LI Jun-Fang2, LIU Chun-Rong2, SUN Xiu-Li2, TANG Yong2*   

  1. 1. Anhui Key Laboratory of Functional Molecular Solids, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, China;
    2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
  • Received:2010-10-18 Revised:2011-01-09 Online:2011-03-10 Published:2011-02-23
  • Contact: Yong TANG E-mail:tangy@mail.sioc.ac.cn
  • Supported by:

    国家自然科学基金(批准号: 20904049)资助.

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被引次数

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摘要： 利用（O-NX）TiCl3非茂聚烯烃催化剂实现了乙烯和4-(10-十一烯)-吡啶的共聚合反应，成功将吡啶基团负载在聚乙烯上，在5mol%负载的吡啶和1mol%卟啉铁的催化作用下，此聚合物作为负载型催化剂可以高效地催化重氮化合物与双拉电子Michael受体的反应，高产率、高非对映选择性地得到二氢呋喃衍生物. 催化剂至少可以回收3次，反应收率均大于90%. 该催化反应具有分离和纯化方便、催化剂可回收利用、催化剂无挥发性的特点.  

关键词: 非茂聚烯烃催化剂, 负载催化剂, 叶立德, 二氢呋喃环化反应

Abstract: The ylide reaction is one of the most useful approaches in forming ring compounds, and highly efficient catalysis of ylide reaction becomes one of the important frontiers in organic synthetic research. Polymer supported catalysis with tunable loading may increase the efficiency of the catalysis and avoid the volatilization of the ylide catalysis which might be savory and poisonous. In the presence of catalytic (O-NX) TiCl3 and MMAO, 4-(undec-10-enyl)pyridine was triumphantly inserted into the polyethylene chains. This PE supported pyridine proved to be an excellent recoverable and reusable organocatalyst. In the presence of catalytic amount of PE-supported pyridine and Fe(Tcpp)Cl, α-ylidene-β-diketones reacted with diazoacetate affording dihydrofurans respectively in up to 96% yield with high diastereoselectivities. The catalyst could be easily recovered after the reaction by cooling the reaction mixture to room temperature because the solubility of the PE-supported catalyst is dependent on the temperature and comonomer content. The yield of the reaction was almost maintained with excellent selectivity which was higher than 90% in 3 runs. This application allowed PE to be used as a cheap, readily prepared, easy separation, no-volatility, low noxious and recoverable catalyst support.

Key words: Non- Metallocene catalysts, Supported catalysts, Ylide, Dihydrofuran cyclization reaction

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