基于胆甾酸骨架构建新一类炔基和叠氮拓扑化学反应体系

With the specific arrangement of functional groups in confined space, topochemical reactions can lead to products with highly controlled structures in terms of high stereoregularity and regioselectivity and no catalysts are needed. The development of a new kind of topochemical reaction has attracted increasing attentions due to their potential applications in numerous areas, but represents a great challenge. In this project, a new topochemical reaction of alkyne and azide groups will be systematically investigated. By co-crystal engineering and supramolecular assembly, the naturally occurring scaffolds of bile acids with the characteristic of facial amphiphilicity and easy to form ordered structures are applied to impose the necessary structural parameters upon alkyne and azide groups. After that we will explore their requisite structural parameters and the regioselectivity of triazole products as well as the reaction kinetics and reaction mechanism. The implementation of this project will allow for the development of a new efficient “green” topochemical reaction for producing products with highly regioselectivity without using catalysts and also can reach further understanding of the rational design principle of topochemical reaction. This research will be useful for the development of material science et al.

拓扑化学反应的基团在受限空间中满足特定排列结构时，无需使用催化剂可高效转化为高区域选择性和立体选择性产物。发展新一类拓扑化学反应是一项极富挑战而有意义的工作。基于已取得的研究成果，本项目拟对炔基和叠氮的拓扑化学反应进行系统研究。通过设计合成一系列胆甾酸含炔基或叠氮的衍生物，以具有面式两亲性特点和易于形成有序排列结构的天然胆甾酸分子为骨架，结合混合两亲性分子共结晶和共组装的方法，使炔基和叠氮在胆甾酸有序结构中形成有利于拓扑化学反应的排列结构，探索炔基和叠氮发生拓扑化学反应的最优空间排列参数和三唑产物的区域选择性，进一步探讨其反应动力学特征和反应机理。本项目的设立和开展，有望发展新一类环保、简单、高效、无催化剂且产物具有高度区域选择性的拓扑化学反应，也将使我们对拓扑化学反应合理设计方面获得深层次的理解和认识，为该类反应在功能材料等领域的应用提供有价值的信息。

拓扑化学反应的基团在受限空间中满足特定排列结构时，无需使用催化剂可高效转化为高区域选择性和立体选择性产物。发展新一类拓扑化学反应是一项极富挑战而有意义的工作。该项目主要以胆甾酸为骨架构筑了炔基和叠氮的拓扑化学反应体系。研究表明，胆甾酸的骨架有序排列有助于形成炔基和叠氮有序排列结构，在加热或者加压条件下可以快速高效得到三唑基团连接的胆甾酸高分子结构，实现无溶剂、无催化剂条件下的高效拓扑化学反应。实现高区域选择性的炔基和叠氮拓扑化学反应，需满足两基团之间最小距离小于3.7 Å，且炔基和叠氮头尾、尾尾或头头平行排列方式将决定所得三唑基团的1,4-和1,5-区域选择性。炔基和叠氮拓扑化学反应体系的发展和完善，有助于简单、快速、高效的制备高纯度的生物功能材料，为高分子的高效合成提供一个新的方法。