机械研磨条件下笼状化合物和共价有机框架的绿色合成

Solvent-free organic reaction under mechanical milling conditions is one of the important areas of organic chemistry, and attracts increasing attention of organic chemists. This project will use the easily available starting materials such as cyclotricatechylene, pentaerythritol, aryl diboronic acids, 4-formylphenylboronic acid, dialdehydes, diamines, amino porphyrins or amino metalloporphyrins, and tetrakis(4-aminophenyl)methane to efficiently construct a series of cage compounds, molecular capsules, and covalent organic frameworks under solvent-free and mechanical milling conditions. The key steps for the multicomponent reactions are the condensations of boronic acids with diols and of aldehydes and amines. The dimensions and shapes of the to-be-synthesized cage compounds can be modulated by the geometry of building blocks, and both ellipsoidal and octahedral cage compounds can be constructed. In addition, a fullerene molecule may be selectively encapsulated into the cage during the synthesis process. Meanwhile, two-dimensional and three-dimensional covalent organic frameworks can be prepared depending on the structures of the employed starting materials. These cage compounds, molecular capsules, and covalent organic frameworks with novel structures and unique shapes may have intriguing properties and find applications in molecular recognition and catalysis.

机械研磨下的无溶剂有机反应是绿色有机合成研究的内容之一，受到越来越多有机化学工作者的关注。本项目将研究在无溶剂和机械研磨条件下，由苯六酚、季戊四醇、芳基双硼酸、4-醛基苯硼酸、二醛、二胺、氨基卟啉（或氨基金属卟啉）、四(对氨基苯基)甲烷等易得的原料，通过硼酸与二醇的缩合和醛与胺的缩合作为关键步骤的多组分反应，高效构筑一系列笼状化合物、笼状胶囊化合物和共价有机框架等功能大分子和多孔有机材料。通过选择不同尺寸大小和几何构型的构筑模块，合成的笼状分子将具有内腔尺寸可调的椭球型和八面体型结构，还可以将富勒烯分子选择性地封装在笼状分子内，而拟合成的共价有机框架具有结构规整的二维平面和三维立体结构。这些结构新颖的大分子和有机材料将具有独特的性能，在分子识别和催化方面具有潜在的应用前景。

机械研磨技术应用于无溶剂有机反应越来越引起化学家们的浓厚兴趣。本项目集中研究了在机械研磨条件下笼状化合物、轮烷、锁烃等功能大分子的无溶剂有机合成，以及若干新颖无溶剂有机反应得到类别多样性的有机化合物。1,3,5-三(4-硼酸)苄基-2,4,6-三烷基苯与季戊四醇定量地生成笼状化合物，铜催化的通过点击化学由炔烃和叠氮化合物生成贯穿冠醚的轮烷化合物，通过冠醚与对二苄溴和联吡啶等在KPF6存在下生成吡啶盐类与冠醚互穿的锁烃产物。还研究了在机械研磨条件下膦酰化苯并噻唑/噻唑、3,2’-吡咯啉基螺氧化吲哚、2,3-二氢吡咯/吡咯、二氢喹啉类化合物、螺环咪唑啉、邻卤代乙酰苯胺、二苯并内酯、菲啶酮、2-氨基苯胺、1,2-二取代苯并咪唑、茚酮、异噁唑等类别的有机化合物的合成。