过渡金属催化的硼化，分子内环化，硼官能团迁移串联反应研究

In recent years, Suzuki cross-coupling reactions have been developed to a significant method in organic synthesis chemistry. Consequently, the synthesis of organoboron compounds, which are required by Suzuki coupling reactions, attract widespread concern. At present, series of construction methods of carbon-boron bond have been contributed by numerous organic chemists. Inspired by the mechanism of Miyaura borylation reaction and transition metal catalyzed functional groups translocation, this project aims to develop transition metal-catalyzed reactions proceeding with translocation of boron functional groups. The design gives a thought to atom economy as well, in which all substrates will be converted to product. Ortho-amino (hydroxy or sulfhydryl) phenylacetylene substrates will perform serial boronation, intermolecular cyclization and translocation of boron functional groups catalyzed by transition metal. By this method, 3-indole boronic ester, 3-benzofuran boronic ester as well as 3-benzothiophene boronic acid derivatives can be achieved, which are well known difficult to synthesize through traditional methods. This method will expend current researches of C-B bond construction and functional group translocation. Moreover, this reaction system stands for a novel type of activation and boronation of C-H bond. C-B bond can be constructed on respective C3 position of benzofuran and indole substrates without halide substituents, enriching synthesis methodology of heterocyclic boron ester derivatives. In comparison, traditional C-H bond activation is insufficient on the same site.

近年来，Suzuki交叉偶联反应被发展成为一种有机合成的重要手段。与此同时，参与Suzuki反应所必须的有机硼物种的合成也得到了化学家的广泛关注。目前，化学家已发展了一系列较为成熟的构建C-B键的方法。本项目依据原子经济性这一概念，结合Miyaura硼化反应与过渡金属催化的官能团迁移反应，设计过渡金属催化的硼化/分子内环化/硼官能团迁移串联反应过程，即以邻胺基（羟基或巯基）苯乙炔作为反应底物，构建常规方法较难合成的3位吲哚硼酸酯、3位苯并呋喃硼酸酯以及3位苯并噻吩硼酸酯衍生物，同时拓展C-B键构建和官能团迁移这两个重要的研究领域。更为重要的是，这一反应模式可以看作是一类新颖的C-H键活化硼化反应，在同样不需要卤代物前体的情况下，弥补传统C-H键活化硼化反应自身反应位点受限的不足，在苯并呋喃和吲哚的3位构建C-B键，丰富了杂环硼酯类衍生物的合成方法学。

有机硼物种作为有机化学中重要的合成砌块，广泛应用于如Suzuki等交叉偶联剂反应中。本项目依据原子经济型原则，结合Miyaura硼化与过渡金属催化的官能团迁移反应，设计过渡金属催化的硼化/分子内环化/硼官能团迁移串联反应过程。即以邻胺基（羟基或巯基）苯乙炔作为反应底物，构建常规方法较难合成的3位吲哚硼酸酯、3位苯并呋喃硼酸酯以及3位苯并噻吩硼酸酯衍生物，同时拓展C-B键构建和官能团迁移这两个重要的研究领域。更为重要的是，这一反应模式可以看作是一类新颖的C-H键活化硼化反应，在同样不需要卤代物前体的情况下，弥补传统C-H键活化硼化反应自身反应位点受限的不足，在苯并呋喃和吲哚的3位构建C-B键，丰富了杂环硼酯类衍生物的合成方法学。