One‐Handed Helical Tubular Ladder Polymers for Chromatographic Enantioseparation**
One‐Handed Helical Tubular Ladder Polymers for Chromatographic Enantioseparation**
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用于色谱对映分离的单手螺旋管状梯形聚合物**
DOI：
10.1002/anie.202218297
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Ikai Tomoyuki
中科院分区：
文献类型：
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作者：
Zheng Wei;Oki Kosuke;Saha Ranajit;Hijikata Yuh;Yashima Eiji;Ikai Tomoyuki
通过对含有6，6′‐linked‐1，1′‐spirobiindane‐7，7′‐diol‐based手性单体单元的无规卷曲前驱体进行炔基苯环反应，合成了具有π-富电子圆柱螺旋腔的无缺陷单手收缩螺旋管状梯形聚合物。得到的紧密缠绕螺旋管状梯形聚合物对多种具有点、轴和平面手性的手性疏水芳香族化合物表现出极高的对映体分离能力。无规卷曲前驱体聚合物和类似的刚性棒状延伸螺旋带状梯形聚合物，没有内螺腔，没有拆分能力。分子动力学模拟表明，在紧密扭曲的管状螺旋梯形结构中形成的富含π电子的圆柱形螺旋空腔是产生高对映体分离能力的关键，通过这种能力，手性芳香族化合物可以通过特定的π-π和/或疏水相互作用来选择性地包封。
Defect‐free one‐handed contracted helical tubular ladder polymers with a π‐electron‐rich cylindrical helical cavity were synthesized by alkyne benzannulations of the random‐coil precursor polymers containing 6,6′‐linked‐1,1′‐spirobiindane‐7,7′‐diol‐based chiral monomer units. The resulting tightly‐twisted helical tubular ladder polymers showed remarkably high enantioseparation abilities toward a variety of chiral hydrophobic aromatics with point, axial, and planar chiralities. The random‐coil precursor polymer and analogous rigid‐rod extended helical ribbon‐like ladder polymer with no internal helical cavity exhibited no resolution abilities. The molecular dynamics simulations suggested that the π‐electron‐rich cylindrical helical cavity formed in the tightly‐twisted tubular helical ladder structures is of key importance for producing the highly‐enantioseparation ability, by which chiral aromatics can be enantioselectively encapsulated by specific π‐π and/or hydrophobic interactions.