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摘要：芳基硼酸的化学转化经历了几十年的发展，目前已经实现C-B键向C-C键、C-O键、C-N键、C-S键、C-X键转化。其中Suzuki偶联反应已经得到了学术界和工业界的广泛应用，正因为此Akira Suzuki教授和Richard F. Heck教授以及Ei-ichi Negishi教授一起分享了2010年的诺贝尔化学奖。与构建C-C时常采用金属钯为催化剂不同，在C-O键、C-N键和C-S键的形成反应中多采用金属铜盐作为催化剂，且反应条件温和，这较传统的 Ullmann偶联反应已有了较大改进，也必将在今后的合成化学中占有重要地位。但是目前芳基硼酸的转化也面临一些局限性，比如在C-C键的形成反应中多数关注的是C-Csp2，对于C-Csp3的形成过程研究的较少。鉴于铜催化剂的廉价易得和丰富的反应化学，我们期望能够通过本论文的研究实现芳基硼酸的高效烷基化反应，进一步拓展芳基硼酸的反应化学。我们以α-溴代乙腈为烷基化试剂，在吡啶亚胺作为配体条件下，在阳离子铜催化下，以中等收率得到了芳基硼酸进行氰甲基化的产物，反应还需进一步优化。在论文研究开展的过程中，意外地发现α-溴代乙腈不仅是腈甲基化试剂，还可以作为溴化试剂高效的实现芳基硼酸的溴化反应，我们通过配体调节，当以1,10-菲咯啉作为配体，氯化亚铜作为催化剂时，反应以中等到优秀的收率得到了芳基硼酸溴化产物。62063
毕业论文关键词：芳基硼酸，铜，腈甲基化，溴化
Copper-catalyzed Cyanomethylation and Bromination of Aryl Boronic Acids
Abstract：C-B bond represents one of the most versatile chemical bond in organic synthesis, which could be transformed to C-C, C-O, C-N, and C-S bond under mild reaction conditions. Until now, a variety of transformations have been achieved based on this chemistry. Among them, Suzuki–Miyaura coupling reaction has been widely employed both academically and industrially. In contrary to the construction of C-C bond, in which palladium catalyst is broadly used, building of C-O, C-N, and C-S bonds from the corresponding C-B bond are mostly conducted with copper salts as catalyst. Although this field has achieved great improvement in the last decades, some limitations are still existed in C-B chemistry, for instance, fewer examples focuses on the construction of C-Csp3 from C-B compared to C-Csp2 bonds. Due to the abundance and easy availability of copper catalyst along with its robust chemistry, we expect to develop a copper-catalyzed system to realize efficient transformation of C-B to C-Csp3 bonds in this dissertation. With α-bromoacetonitrile as the alkylation reagent, we obtained the cyanomethylation product with pyridine-imine as the ligand in moderate yield, which need to be further optimized. During the investigation of the cyanomethylation of phenyl boronic acid, we discovered a catalytic system to transfer C-B bond to C-Br bond unexpectedly. With the choice of 1,10-phenanthroline as the ligand and copper chloride as the catalyst, we obtained the bromination products in moderate to excellent yields.
Key words：Aryl boronic acid, Copper, Cyanomethylation, Bromination
1. 前言
1.1 引言.1
1.2 C-B键向C-C键的转1
1.2.1 C-B向C-Csp转化，芳基硼酸的氰基化反应 .1
1.2.2 C-B向C-Csp2转化，Suzuki 交叉偶联反应2
1.2.3 C-B向C-Csp3转化.4
1.3 C-B键向C-X键的转化.5
1.3.1 C-B键向C-O键的转化5
1.3.2 C-B键向C-N键的转化7
1.3.3 C-B键向C-S键的转化8
1.3.4 C-B键向C-X键的转化8
1.4 论文立意.10
2. 实验部分
2.1 仪器和试剂10
2.1.1 本实验所用试剂 11
2.1.2 本实验所用仪器12
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