基于新型烯基氧化锍叶立德的[4+3]环加成反应用于七元碳环骨架构建的研究

七元碳环骨架合成新方法的开发是众多有机化学家研究的焦点。已有的合成方法存在底物结构复杂、全碳合成子类型少、产物官能团多样性不足等缺点。烯基氧化锍叶立德是一类新型的乙烯基卡宾前体底物，与乙烯基重氮化合物相比具有明显的结构和反应模式差异，具有结构新颖、合成简捷、热力学稳定性高、反应模式多样等优点，可作为全新的三碳合成砌块构建多种类型的有机分子。申请人前期研究发现该合成子可通过[4+3]环加成反应构建具有官能团多样性的七元碳环骨架分子，基于此，本项目拟开展烯基氧化锍叶立德的新型化学转化用于七元碳环骨架的构建。具体研究内容为：① 过渡金属催化烯基氧化锍叶立德的[4+3]环加成反应；② 协同催化的串联反应策略用于烯基氧化锍叶立德的[4+3]环加成反应研究；③ 天然产物和药物分子结构片段的合成和修饰。本研究的顺利开展将为天然产物化学和药物化学领域研究七元碳环骨架分子的合成和修饰提供一条高效的方法。

The development of new methods for the synthesis of seven-membered carbocyclic skeletons is the focus of many organic chemists. The existing synthesis methods have the disadvantages of complicated substrate structure, few types of all-carbon synthons, and insufficient product functional group diversities. Vinyl sulfoxonium ylide is a new type of vinyl carbene precursor substrate. Compared with vinyl diazo compounds, it has obvious structure and reaction mode differences. It has the advantages of novel structure, simple synthesis, high thermodynamic stability, and diverse reaction modes, and can be used as a new three-carbon building block to construct various types of organic molecules. The previous study of the applicant found that this synthon could be used to construct a seven-membered carbocyclic skeleton molecule with a variety of functional groups through the [4+3] cycloaddition reaction. Based on the above research, this project intends to carry out a new chemical transformation of vinyl sulfoxonium ylide for the construction of seven-membered carbocyclic skeleton. The specific research contents are: ① Transition metal catalyzed [4+3] cycloaddition reaction of vinyl sulfoxonium ylide; ② Co-catalyzed tandem reaction strategy for [4+3] cycloaddition reaction of vinyl sulfoxonium ylide; ③ Synthesis and modification of natural products and pharmaceutical molecular structures. The successful development of this study will provide an efficient method for the synthesis and modification of seven-membered carbocyclic skeleton molecules in the fields of natural product chemistry and medicinal chemistry.