Ma Chunmiao, Tang Jie, Yu Lu, Wen Kehan, Gan Quan
Hubei Engineering Research Center for Biomaterials and, Medical Protective Materials, Hubei Key Laboratory of Bioinorganic Chemistry & Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, 430074, P. R. China.
Chemistry. 2022 May 16;28(28):e202200834. doi: 10.1002/chem.202200834. Epub 2022 Apr 8.
An asymmetric reaction can be implemented and refined in the helical cavity of aromatic oligoamide sequences. These sequences, which bear a chiral inducer, can fold into helical structures with absolute control of the helical sense, whereby a ketone substrate covalently linked in the cavity can be asymmetrically reduced to diastereomers. The diastereoselectivity of the reduction is highly dependent on the shielding efficiency of the helical cavity. Iterative modifications of the sequence, such as addition and replacement of monomers, can fine-tune the cavity to realize the asymmetric reaction, thereby progressively increasing the diastereomeric excess up to 90 %.
不对称反应可以在芳香族寡聚酰胺序列的螺旋腔中实现并优化。这些带有手性诱导剂的序列能够以绝对控制螺旋方向的方式折叠成螺旋结构，从而使共价连接在腔内的酮底物不对称还原为非对映异构体。还原反应的非对映选择性高度依赖于螺旋腔的屏蔽效率。通过对序列进行迭代修饰，如添加和替换单体，可以对腔进行微调以实现不对称反应，从而逐步将非对映体过量提高到90%。
