有机化学 ›› 2014, Vol. 34 ›› Issue (8): 1523-1541.DOI: 10.6023/cjoc201403003 上一篇    下一篇

综述与进展

LiCl促进的多官能团格氏试剂的制备及应用研究进展

刘雨燕a, 方烨汶a, 张莉a,b, 金小平c, 李瑞丰b, 朱帅汝a, 高浩其a, 房江华a, 夏勤波a   

  1. a 宁波工程学院化学工程学院 宁波 315016;
    b 太原理工大学化学化工学院 太原 030024;
    c 浙江医药高等专科学校基础部 宁波 315100
  • 收稿日期:2014-03-03 修回日期:2014-04-02 出版日期:2014-08-25 发布日期:2014-04-18
  • 通讯作者: 方烨汶,金小平,李瑞丰 E-mail:nbut.fang@gmail.com
  • 基金资助:
    国家自然科学基金(No.21202090)、宁波市科技创新团队(No.2011B82002)、浙江省自然科学基金(Nos.LY12B02001,LQ13B010004)、宁波市自然科学基金(Nos.2011A610123,2012A610123)、钱江人才计(B)(No.2013R10076)、新苗人才计划(No.2011R422008)资助项目.

Advances in LiCl-Promoted Preparation of Polyfunctional Grignard Reagents and the Applications

Liu Yuyana, Fang Yewena, Zhang Lia,b, Jin Xiaopingc, Li Ruifengb, Zhu Shuairua, Gao Haoqia, Fang Jianghuaa, Xia Qinboa   

  1. a School of Chemical Engineering, Ningbo University of Technology, Ningbo 315016;
    b College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024;
    c Department of Basic Education, Zhejiang Pharmaceutical College, Ningbo 315100
  • Received:2014-03-03 Revised:2014-04-02 Online:2014-08-25 Published:2014-04-18
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21202090), the Ningbo Science and Technology Innovation Team (No. 2011B82002), the Zhejiang Provincial Natural Science Foundation of China (Nos. LY12B02001, LQ13B010004), the Ningbo Natural Science Foundation (Nos. 2011A610123, 2012A610123), the Qianjiang Talents Project (B) (No. 2013R10076), and the Xinmiao Talents Program (No. 2011R422008).

自格氏试剂发现以来,含多官能团的格氏试剂合成一直是有机镁合成化学研究的热点和难点. 重点综述了Knochel小组以氯化锂为添加剂,成功地通过三类常用的格氏试剂制备方法(金属镁和有机卤化物的直接氧化加成、卤素-镁交换、C—H键的镁化)合成了一系列含多官能团的格氏试剂. 氯化锂的引入不但解决了官能团的兼容性问题,还提高了格氏试剂的反应活性,从而极大拓展了格氏试剂在合成化学中的应用. 对氯化锂促进型格氏试剂合成的局限和研究前景也进行了探讨和展望.

关键词: 格氏试剂, 多官能团, 氯化锂, 卤素-镁交换, 镁化反应

Since the discovery of Grignard reagents, the synthesis of highly functionalized organomagnesium compounds has been hot but difficult project. In the presence of LiCl, a series of polyfunctional Grignard reagents were successfully prepared by Knochel group via direct oxidative addition of magnesium to organic halides, halogen-magnesium exchange reaction, or direct magnesiation of C—H bond. In the presence of LiCl, the issue of functional group compatibilities was addressed and the reactivity was also enhanced. Consequently, the applications of Grignard reagents in synthetic chemistry were greatly expanded. The limitations and potential research areas for LiCl-promoted synthesis of Grignard reagents are also discussed.

Key words: Grignard reagent, polyfunctional group, lithium chloride, halogen-Mg exchange, magnesiation reaction