基于过渡金属催化的多取代1,2,3-三唑的合成方法学研究

Efficiently regioselective synthesis of multi-substituted 1,2,3-triazoles is an important topic in the triazole chemistry. Based on current progresses of triazole synthesis, our research program will proceed from the transition metal-catalyzed organic reactions and take their advantages and characteristics to achieve the formation of appropriate chemical bonds, in which triazole rings will be constructed. Upon above results, novel methodologies of multi-substituted 1,2,3-triazoles can be established facilely from transition metal-catalyzed multi-step reactions. In the project of our researchs, these triazole-ring-constructed cyclization reactions include: the transition metal-catalyzed N-N bond generation in oxidative cyclization, the tandem reaction of transition-metal catalyzed coupling reaction with Huisgen cycloaddition reaction in the participation of small organic molecules such as amines and alcohols . At the same time, to achieve the success from the above-mentioned synthesis methods of multi-substituted triazoles, intense research will be implemented to investigate and reveal the influence of various factors, which include the type of transition metal salts and its ligands, the steric effect and the electronic effect in these reactions. Meanwhile, the further mechanisms of these reactions could be disclosed. The results of this project contribute to not only the new synthetic methods establishing of the multi-substituted 1,2,3-triazoles but also the insight of the triazole cyclization reactions. The success of our research will supply the experimental and theoretical basis for the further investigate of triazole synthesis via transition metal-catalyzed.

高效地实现多取代1,2,3-三唑的选择性合成是三唑化学中重要的课题。基于三唑的研究现状，本项目研究内容包括从过渡金属催化有机合成反应的优势和特点出发，采用适当的化学键形成而实现三唑环构建，从而建立多取代三唑的合成新方法。这些三唑环构建的环化反应包括过渡金属催化下N-N键合成的氧化环化方法；过渡金属催化下胺及醇等有机小分子参与的偶联反应与Huisgen环加成反应的串联反应。与此同时，为上述多取代三唑合成方法的成功，我们将深入考察和揭示各种因素如过渡金属盐及其配体、反应物料的空间位阻效应和电子效应等对反应结果的影响规律，进一步揭示反应机理。本项目的研究成功，不仅有助于多取代-1,2,3-三唑合成新方法的建立，同时有助于深入理解三唑的环化反应，为今后过渡金属催化三唑合成提供实验基础和理论依据。

1,2,3-三唑是一类重要的五元杂环化合物。至今，该类化合物已在合成化学，医药，农药，材料化学等领域都有着重要的应用。因此，1,2,3-三唑的合成研究受到了广泛的关注。尽管三唑化合物的合成取得了诸多成果，但高效地实现多取代1,2,3-三唑的选择性合成是三唑化学中重要的课题。本项目研究内容对三唑合成新方法进行了深入研究。我们发展了卤代烯烃与芳基叠氮的环加成反应合成多取代的1,2,3-三唑，铜催化下2,4,5-三取代-1,2,3-三唑合成，醛、硝基烷烃和叠氮化钠的三组分反应合成NH-4-取代的1,2,3-三唑的合成方法，还对Ts-醛腙与腈环加成反应合成1,2,3-三唑以及苄基叠氮脱氮反应等方面进行了研究，并取得了部分研究成果。这些研究成果为三唑合成，尤其是一些结构独特的三唑的合成，提供了新的方法。