稀土金属促进的炔烃及联烯的小分子活化反应研究

The activation of small molecules promoted by rear earth metals is the most important field in organometallic chemistry and also has attracted great attention from organic chemists. The main foucs of the proposed research is the study of new reactions of alkynes and allenes using rare earth metals as the catalysts through novel train of thought and strategy. Intensive research during the last two years in our laboratory proved that wide variety of rare earth metals which display certain degree of catalyse behavior, are remarkably efficient for the activation of unsaturated bonds. Based on these results, we will try to find new methodologies to improve the catalytic efficiency of rear earth metals 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 catalyst and substrate, 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 organic reactions catalyzed by rear earth metals. Moreover, we will obtain some greener and convient synthetic methodologies with high performance which are very useful for the synthesis of complex compounds.In this way the fruits of the research will be exposed to a broader audience,thereby, helping overlap between the alkynes, allenes and rear earth metal chemistry. Therefore,this research has important significance not only in basic theory aspect, but also in potential application field.

稀土金属促进的小分子活化反应是金属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。本项目以炔烃和联烯为研究对象，探索以新的思路和策略建立和发展稀土金属催化的炔烃及联烯的反应新思路和新途径， 研究提高稀土金属催化效率的新方法，理解结构与反应性能之间的关系，揭示催化剂与底物之间的作用对反应选择性的影响，阐明催化反应的基本规律，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，为发展先进的稀土金属催化的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，以其来指导复杂化合物的合成。该研究既丰富了炔烃、联烯化学，又拓宽了稀土金属在有机化学中的应用。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。

稀土金属促进的小分子活化反应是金属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。本项目以炔烃和联烯为研究对象，发展了稀土金属催化的炔烃的活化反应，并深入探讨了各反应的可能机理。首先，合成了一系列炔烃及联烯化合物，并详细研究了其在稀土金属催化下的反应。发现，稀土金属可以活化二茂铁炔烃，从而与芳香醛及芳香胺实现三组分加成异构化反应，合成了一系列含二茂铁的喹啉化合物。此外，稀土金属Y(OTf)3可以催化三级炔丙醇与肼发生串联炔丙基取代/氮杂-Meyer–Schuster重排反应，高立体选择性地得到多取代的α,β-不饱和腙类化合物。在此基础上，还发展了Yb(OTf)3催化的炔丙醇与苯并恶唑的开环官能化反应，可以高原子经济性地制备含醛基、羟基及炔丙胺的多取代苯类化合物。期间，发展了CuBr促进的端炔与羰基醛反应，得到了端炔形式上的氢酰基化1,2-二羰基-3-烯化合物，并成功将其应用到吲哚稠环化合物的合成。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。我们发现，二茂铁联烯与重氮化合物、芳基碘化物在Pd催化下可以发生三组分偶联反应，成功构筑含二茂铁基团的1,3-丁二烯化合物；在此基础上，还发展了Pd催化的二茂铁联烯、芳基碘化物与羧酸的三组分反应，顺利得到含二茂铁基团的烯丙基酯类化合物。此外，我们还发展了Rh2(OAc)4催化的重氮化合物的分子内2,3-迁移反应。本项目的实施达到了预期目标，同时也存在一些问题，比如没有解决稀土金属对联烯的活化，我们将在接下来的工作中进行充实研究。