Locking Interconversion of Aromatic Oligoamide Foldamers by Intramolecular Side-chain Crosslinking: toward Absolute Control of Helicity in Synthetic Aromatic Foldamers
Locking Interconversion of Aromatic Oligoamide Foldamers by Intramolecular Side-chain Crosslinking: toward Absolute Control of Helicity in Synthetic Aromatic Foldamers
复制标题
通过分子内侧链交联锁定芳香族低酰胺折叠体的互变：实现合成芳香族折叠体螺旋度的绝对控制
DOI：
10.1002/chem.201700134
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Jiang Hua
中科院分区：
文献类型：
--
作者：
Zheng Lu;Yu Chengyuan;Zhan Yulin;Deng Xuebin;Wang Ying;Jiang Hua
通过分子内闭环烯烃复合反应，将一系列8 -氨基- 2 -喹啉羧酸折叠物串接在一起，生成具有不同长度烃侧链的约束芳香折叠物。研究清楚地表明，侧链交联剂能够在CDCl3中，甚至在C2D2Cl4中，在很宽的温度范围内完全锁定装订的芳香折叠物的相互转换。因此，具有短碳氢化合物交联剂的折叠物可以很容易地通过硅胶色谱分离，从而生成具有稳定的绝对单手螺旋度的折叠物。但具有较长交联剂的装订折叠体即使用手性高效液相色谱也不可分离，这可能是由于非对映体的偶然极性相同。
A series of foldamers of 8‐amino‐2‐quinoline carboxylic acid were stapled by intramolecular ring‐closing olefin metathesis to generate the constrained aromatic foldamers with varying lengths of hydrocarbon side‐chains. Investigations clearly revealed that the side‐chain crosslinkers are capable of completely locking the interconversions of the stapled aromatic foldamers over a wide range of temperatures in CDCl3, even in C2D2Cl4. Hence, the stapled foldamers with the short hydrocarbon crosslinker can be easily separated by silica‐gel chromatography to generate foldamers with stable, absolute one‐handed helicity. But the stapled foldamer with the longer crosslinker is inseparable even by chiral HPLC presumably due to the fortuitous identical polarity of the diastereomer.