licl促进的多官能团格氏试剂的制备及应用研究进展.docVIP

有机化学 DOI: 10.6023/cjoc201403003 综述与进展 Chinese Journal of Organic Chemistry REVIEW 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 (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) 摘要 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 Advances in LiCl-Promoted Preparation of Polyfunctional Grignard Reagents and the Applications Liu, Yuyana Fang, Yewen*,a Zhang, Lia,b Jin, Xiaoping*,c Li, Ruifeng*,b Zhu, Shuairua Gao, Haoqia Fang, Jianghuaa Xia, Qinboa (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) Abstract 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 ex- panded. The limitations and potential research areas for LiCl-promoted synthesis of Grignard reagents are also discussed. Keywords Grignard reagent; polyfunctional group; lithium chloride; halogen-Mg exchange; magnesiation reaction RMgX (X 为卤素, R 为烃基)和RMgR 等有机镁试 年代的Kumada-Corriu 反应掀起了格氏试剂在过渡金属 剂, 通常称之为格氏试剂(Grignard Reagent), 由法国化 催化的C－C 偶联反应中应用的热潮[3]. 学家格林尼亚(Francois Agust