官能化二茂铁联烯化合物的合成及其立体选择性加成反应研究

The ferrocene chemistry as well as the allene chemistry are the most important fields in organic chemistry and also have attracted great attention from organic chemists. The main foucs of the proposed research is the study on the synthesis of new functional ferrocenylallenes through novel train of thought and strategy. Intensive research during the last two years in our laboratory proved that monosubstituted ferrocenylallene can achieve high regio- and stereoselective electrophilic addition reactions. Based on these results, we will try to find the influence of the ferrocene and the functional group on the stereoselectivities of the additions of these functional ferrocenylallenes and also have a better understanding of the relationship between the substrate structure and reactivities. Through the implementation of this project, we look forward to disclose the effect on the reaction selectivities from the interaction of ferrocene and functional group, and then explain the basic principles as well as the possible mechanism of these new reactions. The results from this proposed research will provide us the important theoretical guidance for the efficient and stereoselective new organic reactions based on the functional ferrocenylallenes. Moreover, we will obtain some greener and convient synthetic methodologies with high performance which are very useful for the synthesis of ferrocene-containing complex compounds.In this way the fruits of the research will be exposed to a broader audience,thereby, helping overlap between the allenes and ferrocene chemistry. Therefore,this research has important significance not only in basic theory aspect, but also in potential application field.

二茂铁化学以及联烯化学是有机化学的重要研究领域，一直备受有机化学家的广泛关注。本项目以官能化的二茂铁联烯为研究对象，探索以新的思路和策略建立和发展含官能团的二茂铁联烯化合物的合成新途径,研究二茂铁与不同官能团对该类新型联烯化合物的加成反应的立体选择性影响，理解结构与反应性能之间的关系，阐明二茂铁与官能团在控制反应立体选择性中的作用规律，探讨反应的可能机理，以期实现在原理和方法层次上的创新，为发展以官能化的二茂铁联烯为基础的高效、高选择性的新型有机反应提供理论指导，得到具有创新性的研究结果，获得高效、绿色、便捷的有机合成方法，以其来指导含二茂铁基团的复杂化合物的合成。该研究既丰富了茂金属化学，又拓宽了联烯的研究领域。因此，本项目的实施不论对理论研究还是潜在的应用方面都有重要意义。

二茂铁化学以及联烯化学是有机化学的重要研究领域，一直备受有机化学家的广泛关注。本项目以官能化的二茂铁联烯为研究对象，设计合成含官能团的二茂铁联烯化合物，并深入研究其立体选择性加成反应。首先，合成了一系含磷酸酯的二茂铁联烯化合物，并详细研究了其与氮、氧等亲核试剂的立体选择性加成反应,高区域和立体选择性地得到了一系列含二茂铁和磷酸酯的四取代烯烃化合物。另外，研究发现，在氟离子存在下，该官能化联烯化合物可以进行分子内环化，得到环状四取代烯烃。在此基础上，还发展了一个新颖的碱促进的芳基联烯酮与吲哚化合物的串联环化芳构化反应。期间，发展了Cu催化的二茂铁炔与吡啶醛及胺的多组分串联反应，得到了含二茂铁的吲哚啉化合物。在本项目研究过程中，我们也得到了一些意外的、有意义的研究结果。我们实现了一系列基于炔基联苯酚的串联去芳构螺环化反应，得到了各种官能化的螺环环己二烯酮化合物。项目共发表SCI论文12篇，获授权国家发明专利3项。