镁格氏试剂和α-卤代酮、酯的反应的研究及其铜催化构建苯并噁嗪-3-酮类化合物.pdfVIP

镁格氏试剂与α- 卤代酮、酯的反应研究及铜催化构建苯并噁嗪-3-酮类化合物 中文摘要 中文摘要 本论文由两部分组成： 1. 镁试剂是一种活泼的有机金属试剂，与α- 卤代羰基化合物的反应，很难停 留在环氧化合物阶段。很幸运，我们发现通过控制条件，可使烯丙基溴化镁试剂 与 α- 卤代酮反应，停留在环氧化合物阶段，而不进行重排反应或进一步的亲核加 成反应，拓展了镁试剂在有机合成中的应用。 2. 近年，Ullman 类型交叉偶联反应通过“一锅法”串联应用到杂环化合物的 合成中。而杂环化合物广泛存在于许多有生理活性的天然产物、药物、农药以及 具有电子性能的材料中。传统的Ullman 交叉偶联反应一般需要化学当量的铜盐和 富电子的配体。我们以邻碘苯酚和氯乙酰氯合成 2-氢- 1,4-苯并噁嗪-3-酮为例，对 此进行了改进，探索出一种无需加入配体也能较好的催化交叉偶联反应构筑杂环 化合物的方法。 关键词：镁格氏试剂、环氧化合物、铜催化、交叉偶联、杂环化合物 作 者：范丽媛 指导教师：张松林 教授 I 英文摘要 镁格氏试剂与α- 卤代酮、酯的反应研究及铜催化构建苯并噁嗪-3-酮类化合物 The Studies of the Reactions of Magnesium Reagents with α-Halo Ketone or Ester and Construction of Benzoxazin-3-one Derivatives via Copper-Catalyzed Coupling Reactions Abstract This thesis includes two chapters: 1. Organomagnesium reagent is one of the active organometallic reagents. A series of reactions of α-halocarbonyl compounds with organomagnesium reagents have been investigated for a long time. However, epoxides were obtained diffficultly. Fortunately, the only products epoxides were obtained in the reaction of allyl magnesium bromide reagents with α-halo ketones under the proper conditions, without further rearrangement or the nucleophilic addition reaction. This method broardens the application of magnesium reagent in the organic synthesis. 2. Recently, much more attention was payed to the one-pot syntheses of various useful heterocyclic compounds through the Ullman coupling reaction. And heterocyclic compounds have always been a vital part in many natural pharmaceticals, drug and electro