论文总字数：25432字

摘 要

由过渡金属催化的有机金属试剂交叉偶联反应是有机化学中快速构建C-C键或延长碳链的常用方法之一。而有机铟金属试剂作为其中一种较为温和的亲核试剂，与其它常见的有机金属试剂相比（例如有机锂、有机镁、有机锌试剂），它因具有易制备和处理、对空气和水的兼容性，较高的化学或区域选择性以及低毒性等优点而受到广泛关注。在许多偶联反应之中，它也展现出了极佳的官能团兼容性，不会与羰基、氰基、硝基、羟基和氨基等活泼官能团发生副反应，同时还对质子溶剂具有耐受性。

本文首先对有机铟金属试剂的诸多特点及其合成方法进行了描述，之后结合课题组的研究进展，以镍(Ⅱ)作为催化剂通过分步法和铟直接插入法来实现烯丙基卤化物与芳基卤化物间C-C键的构建。在研究过程中选取烯丙基溴、铟粉和对碘苯甲酸乙酯作为模板反应的底物，依次对催化剂、温度以及配体进行筛选以优化反应条件，并最终确定了第二步反应的最佳条件：使用烯丙基铟试剂与芳基卤化物，在10 mol%的Ni(PPh₃)₂Cl₂的催化条件下，在DMF中于60 ^oC下反应12小时。而且在最优反应条件下得到的烯丙基取代芳基化合物的最高核磁产率为78%。在考察底物通用性和范围的过程中，烯丙基铟试剂与带有吸电子基团取代的芳基卤化物的偶联反应能有效进行，产率中等至高。同时，活性较低的芳基氯化物和溴化物也可参与反应。此外，在应用于杂环化合物的过程中，溴代喹啉在最优反应条件下可以很好地进行反应。尤其值得一提的是，有机铟试剂对活泼的官能团也具有耐受性，这也使得这些产物有可能进行进一步的修饰。因而此反应可以为芳环上引入烯丙基提供一种有效的合成途径，并且在研究过程中所有的产物结果均通过¹H NMR、¹³C NMR方法进行表征。

关键字：烯丙基铟试剂 烯丙基化 镍催化 交叉偶联

Nickel-Catalyzed Cross-Coupling Reactions of Allylindium Reagents with Aryl Halides

Abstract

The cross-coupling reaction of organometallic reagents which is catalyzed by transition metals is one of the most efficient methods for the rapid construction of carbon-carbon bond in organic synthesis. As one of the mild nucleophilic reagents, organoindium reagents, compared with other common organometallic reagents, such as organolithium, organomagnesium, and organozinc compounds, have aroused extensive attention globally owing to its easy preparation and handling, compatibility with air and water, and high chemo- or regioselectivity and low toxicity. It also exhibits excellent compatibility to functional groups in many cross-coupling reactions, and will not react with reactive functional groups, including carbonyl, cyanide, nitro, hydroxyl, and amino groups, and is even tolerant to protic solvents.

This thesis first describes some features and synthetic methods of organoindium reagents, and as a connection with the research progress of our group, we studied the use of nickel (Ⅱ) as a catalyst to accomplish the construction of carbon-carbon bond between allyl halide and aryl halides by a stepwise method and indium(0) direct insertion method. In the process, allylic bromide, indium(0) and ethyl 4-iodobenzoate were selected as the model substrates to optimize the reaction conditions by screening the catalyst, temperature and ligand. Finally, the optimal reaction conditions were determined to be that allylindium reagent and aryl halide were coupled in the presence of 10 mol% Ni(PPh₃)₂Cl₂ in DMF at 60 ^oC for 12 hours. And the highest NMR yield of allyl-substituted aryl compounds obtained under the optimal reaction conditions is 78%. In the course of investigating the versatility and scope of the substrate, the cross-coupling reaction of the allylindium reagent with aryl halides bearing electron-withdrawing groups can obtain the target product in moderate to high yields. Additionally, less reactive aryl chloride and bromide can also participate in the reaction. What’s more, in the process of applying the method to heterocyclic compounds, 3-bromoquinoline can perform well under the optimal reaction conditions. It is especially worth mentioning that the cross-coupling reaction is compatible to sensitive functional groups, which also makes it possible for these products to be further modified. Therefore, this reaction can provide an effective synthetic route for the introduction of allyl group on the aromatic rings, and all product were characterized by ¹H NMR and ¹³C NMR.

Key Words: Allylindium reagents; Allylation; Nickel-catalyzed; Cross-coupling

目 录

摘 要 I

ABSTRACT II

第一章 文献综述 1

1.1 前言 1

1.2 有机铟金属试剂的合成研究 2

1.2.1 转金属化法 2

1.2.2 直接插入法 3

1.3 有机铟试剂在有机化学中的应用 5

1.3.1 烯丙基铟试剂 5

1.3.2 芳基铟试剂 6

1.3.3 烷基铟试剂 7

1.3.4 苄基铟试剂 8

1.3.5 本文研究内容 9

第二章 镍催化烯丙基铟试剂与芳基卤化物的偶联反应 11

2.1 前言 11

2.2 反应条件优化 11

芳基卤化物范围扩充 14

第三章 实验部分 17

3.1 实验试剂与仪器 17

3.2 实验步骤 19

3.3 产物结构表征数据 19

第四章 总结与展望 23

4.1 总结 23

4.2 展望 23

参考文献 25

附录 29

本科阶段科研成果 33

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