Chiral 3D Covalent Organic Frameworks for High Performance Liquid Chromatographic Enantioseparation
Chiral 3D Covalent Organic Frameworks for High Performance Liquid Chromatographic Enantioseparation
复制标题
用于高效液相色谱对映体分离的手性 3D 共价有机框架
DOI：
10.1021/jacs.7b12110
复制
发表时间：
2018-01-24
影响因子：
15
通讯作者：
Cui, Yong
中科院分区：
文献类型：
--
作者：
Hang, Xing;Huang, Jinjing;Cui, Yong
尽管由于丰富的主客体化学性质，它们在对映选择性过程中具有巨大的前景，但构建具有手性三维（3D）结构的共价有机框架（COF）仍然是一个挑战。在这里，我们报道了通过对映体纯2倍对称TADDOL衍生的四醛与四面体四(4-苯芳基)甲烷的亚胺缩合，自下而上合成3D手性COF的第一个例子。亚胺键合成后氧化后，框架转化为酰胺连接的 COF，保留了结晶度和永久孔隙率，并增强了化学稳定性。所得同构COF具有4重互穿类金刚石开放框架，具有手性二羟基助剂装饰的管状通道：两种COF均可用作高效液相色谱的手性固定相，以对映体分离外消旋醇，并且与原始框架相比，氧化COF表现出优异的分离性能。
In spite of their great promise for enantioselective processes due to the rich host guest chemistry, it remains a challenge to construct covalent organic frameworks (COFs) with chiral three-dimensional (3D) structures. Here we report bottom-up synthesis of the first example of 3D chiral COFs by imine condensation of an enantiopure 2-fold symmetric TADDOL-derived tetraaldehyde with a tetrahedral tetra(4-anilyl)rnethane. After postsynthetic oxidation of imine linkages, the framework is transformed into an amide-linked COF with retention :of crystallinity and permanent porosity as well as enhanced chemical stability. The resultant isotructural COFs feature a 4-fold interpenetrated diamondoid open framework with tubular channels decorated with chiral dihydroxy auxiliaries: Both COFs can be Used as chiral stationary phases for high performance liquid chromatography to enantioseparate racemic alcohols, and the oxidized COF shows superior separation performance compared to the pristine framework.