Department of Chemical Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, 152-8552, Japan.
Present address: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
Angew Chem Int Ed Engl. 2017 Nov 20;56(47):14858-14862. doi: 10.1002/anie.201707926. Epub 2017 Oct 18.
Effective induction of preferred-handed helicity of polyacetylenes by pendant mechanically chiral rotaxanes is discussed. Polyacetylenes possessing optically active mechanically chiral rotaxanes in the side chains were synthesized by the polymerization of the corresponding enantiopure [2]rotaxane-type ethynyl monomers prepared by the chiral-phase HPLC separations. The CD Cotton effects revealed that the polyacetylenes took preferred-handed helical conformations depending on the rotaxane chirality. The preferred-handed helix was not disturbed by an additional chiral substituent on the rotaxane side chain. These results demonstrate the significance and utility of mechanically chiral rotaxanes for the effective construction of asymmetric fields.
本文讨论了通过侧链上的手性机械轮烷来有效诱导聚乙炔的优势手性螺旋。通过对通过手性相 HPLC 分离制备的相应对映纯[2]轮烷型乙炔基单体进行聚合，合成了在手性侧链上具有光学活性机械手性轮烷的聚乙炔。圆二色谱（CD）Cotton 效应表明，聚乙炔呈现出依赖于轮烷手性的优势手性螺旋构象。轮烷侧链上的额外手性取代基不会干扰优势手性螺旋。这些结果证明了机械手性轮烷在有效构建不对称场方面的重要性和实用性。
