茂锆苯炔在合成苯并硼烯和苯基邻二硼烷中的应用研究

    硼杂芳环类化合物是一类具有独特性质的有机硼化合物，该化合物作为一类含硼有机 π 共轭体系，是“主族含硼元素有机化学”和“π 共轭体系”的结合。 苯并硼杂环丙烯类化合物是其中的一种含硼 π 杂环化合物，它与苯并环丙烯基 阳离子互为等电子体。虽然早期有较多关于苯并硼杂环丙烯化合物的理论计算 研究，但关于苯并硼杂环丙烯化合物的实验合成研究很少，且绝大多数只是在 Matrix 基质中观测到信号，并未实验获得结构。直到 2018 年， Bettinger 等报导了一例氮杂环卡宾稳定的苯并硼杂环丙烯化合物，然而该加合物的稳定性仍不理想，在室温条件下，一天内全部分解，或在﹣35 °C 条件下，数周内二聚。 除此之外，目前对于无路易斯碱稳定的苯并硼杂环丙烯化合物的合成及其反应性研究，几乎没有报导。因此，成功设计并合成出一类无路易斯碱稳定的苯并硼杂环丙烯并对其进行性质研究，将是一个里程碑式的结果。

    金属茂锆试剂在金属有机化学中具有广泛的应用，它们可以参与环加成、 偶联等各种类型反应。其中，二苯基二茂锆试剂是一类常见的茂锆苯炔类化合 物前体。目前为止，尽管关于茂锆试剂诱导的反应，已经有过较为系统的报导， 但还没有茂锆苯炔类化合物与有机硼烷试剂反应的相关研究。通过研究二苯基二茂锆与卤代硼烷反应，本研究成功获得了首例液相中合成的无路易斯碱加合的苯并硼杂环丙烯分子。同时，对苯并硼杂环丙烯化合物的合成方法进行拓展研究，还获得了多种苯基邻二硼烷类化合物。

    本研究尝试了五种不同的合成策略来合成苯并硼杂环丙烯分子，实验结果表明，只有当二苯基二茂锆试剂与二溴代氨基硼烷反应时，才能成功地合成苯并硼杂环丙烯类化合物。利用二苯基二茂锆试剂与二溴代氨基硼烷，在 80 °C 条件下加热的反应策略，最终以 65%的收率获得了苯并硼杂环丙烯类化合物。 除此之外，还进行了茂锆试剂与不同卤代硼烷的反应适应性研究，获得了多种茂锆半开环类含硼化合物、二硼杂蒽类化合物等，并通过单晶衍射确定了其结构。

    同时，本研究还对苯并硼杂环丙烯分子的合成进行了机理分析，并对苯并硼杂环丙烯化合物进行了反应性研究。二苯基二茂锆试剂在 80 °C 条件下，首先发生 β 氢消除，进而生成茂锆苯炔类中间体。随后与二溴代氨基硼烷反应， 生成茂锆半开环类含硼化合物，再经历 σ 复分解过程，发生盐消除，最后生成苯并硼杂环丙烯。此外，也研究了苯并硼杂环丙烯分子与路易斯碱、小分子异腈、羰基插入的反应。并以 30% 的收率获得了卡宾配位后 1,3−三甲基硅烷基迁移的产物结构、小分子活化插入形成的苯并硼杂五元环的产物结构，并对相 关结构进行了单晶结构表征。

    此外，本研究还对苯基邻二硼烷类化合物的合成及反应性质，进行了分析研究。以往合成苯基邻二硼烷类化合物的方法通常会使用到毒性较大试剂、昂贵的原料和催化剂，或需要复杂工艺等条件。本研究中，通过采用二苯基二茂锆与氯代硼烷反应，在 80 °C 条件下加热后经历盐消除过程，成功合成了多种苯基邻二硼烷类化合物。此外，本研究还对茂锆苯炔类化合物与卤代硼烷反应模式，进行了分析。当二苯基二茂锆类试剂与芳基溴代硼烷反应时，能获得对应的二硼杂蒽类化合物；与硅烷基溴代硼烷反应时，能以 65%的收率获得苯并硼杂环丙烯类化合物；与氯代硼烷反应时，能以37%的收率获得对应的茂锆半开环类含硼化合物及对应的苯基邻二硼烷类化合物。

    总之，本研究通过二苯基二茂锆试剂与二溴代氨基硼烷反应，成功合成了苯并硼杂环丙烯化合物，并对合成的苯并硼杂环丙烯化合物进行反应性研究。 此外，本研究还对茂锆试剂与卤代硼烷反应的方法进行了底物普适性的分析研究。通过调控不同的卤代硼烷试剂及反应条件，本研究成功实现了苯并硼杂环丙烯、苯基邻二硼烷类化合物、苯并硼氮杂环类化合物、二硼杂蒽类化合物和茂锆半开环类含硼化合物的合成，为后续相关化合物的应用研究及开发更多新型含硼 π 杂环类化合物奠定了基础。

    Boron-containing π-heterocyclics are a class of organic boron compounds which exhibit unique properties. Boron-containing organic π-conjugated molecules are a combination of "main group organic chemistry of boron-containing compounds" and "π-conjugated systems". Benzoborirenes are isoelectronic to benzocyclopropenyl cations. Although there were many theoretical calculations on benzoborirenes in the early days. However, there were few experimental synthetic studies on benzoborirenes, and most of these structures could only be observed via signals in the Matrix. Until 2018, Bettinger's group reported a case of benzoboriene stabilized by N-Heterocyclic Carbene (NHC). Nevertheless, the stability of the adduct was still not ideal. It was decomposed completely in one day at room temperature or dimerized in a few weeks at −35 °C. So far, synthesis of a base-free benzoborirene has not been achieved yet. Therefore, it will be a milestone to successfully synthesize and structurally characterize a base-free benzoborirene.    

    Zirconium metallocene reagents are widely used in organometallic chemistry. They can participate in various types of reactions such as cycloaddition, coupling. Among them, diphenylzirconocene reagent is a common precursor of zirconocene benzyne complexes. So far, although there have been systematic reports on the reaction mediateded by zirconocene reagent, there is no research on the reaction of zirconocene benzyne complexes with organoborane reagent. Using Cp2ZrPh2 and amino(dibromo)borane, this thesis presented the first successful solution-phase synthesis of a base-free benzoborirene with a yield of 65%. In addition, the synthesis of benzyldiboranes was developed when Cp2ZrPh2 reacted with other dihaloborane complexes.

    Chapter 3 shows the process of exploring the synthesis of benzoborirene. We designed five different synthesis strategies to synthesize benzoborirene. Finally, the benzoboriene was successfully synthesized using Cp2ZrPh2 and amino(dibromo)borane. In addition, we also studied the reaction suitability of zirconocene reagents with different haloboranes. By expanding the synthetic method, a variety of zirconocene semi-ring-opened boron-containing compounds and diboranthene compounds were obtained, and the related structures were characterized by single crystal diffraction.

    Chapter 4 presents mechanism study and the properties of benzoborienes. At 80 °C, the diphenyl zirconocene reagent eliminates β-hydrogen, and then generates zirconocene benzyne intermediates. Subsequently, it reacts with dibromo-aminoborane to generate zirconocene semi-ring-opened boron-containing compounds, and undergoes a σ metathesis reaction. In addition, we also studied the reaction of benzoboriene with Lewis bases, and the reactions involved in the activation of isonitriles and CO-based small molecules. By activating small molecules, a variety of structures with small molecule insertion were obtained, and the related structures were characterized by single crystal structure.

    Chapter 5 shows the synthesis and properties of benzyldiboranes. The previous synthetic procedures of benzyldiboranes were usually with toxic reagents, expensive raw materials and catalysts, or complex processes. In this paper, by the method of reacting diphenyl zirconocene with haloboranes, we can synthesize various benzyldiboranes. In addition, we analyzed the reaction mode of zirconocene benzyne complexes with haloboranes. When using dibromoarylborane, diboranthenes can be obtained; using amino(dibromo)borane benzoborirene can be obtained with a yield of 65%; using dichloroborane, zirconocene semi-ring-opened boron-containing compounds and benzyldiboranes can be obtained.

    In conclusion, the benzoborirene was successfully synthesized by the reaction of diphenylzirconocene reagent with dibromo-aminoborane, and the reactivity of the synthesized benzoborirene was also studied. On the other hand, benzyldiboranes, diboranthene compounds, zirconocene semi-opened boron-containing compounds were synthesized via adjusting different halogenated borane reagents and reaction conditions. This thesis provides a series of novel methods of benzoborienes, benzyldiboranes, benzoborazepines, diboranthenes, zirconocene semi-ring-opened boron-containing compounds. The synthetic method of these compounds can not only lay a foundation for the subsequent application research, but also can develop more new boron-containing π-heterocyclic systems.

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