Ikai Tomoyuki, Nakamura Koshi, Mizumoto Kosuke, Oki Kosuke, Yashima Eiji
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya, 464-8603, Japan.
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), Kawaguchi, Saitama, 332-0012, Japan.
Angew Chem Int Ed Engl. 2023 May 8;62(20):e202301127. doi: 10.1002/anie.202301127. Epub 2023 Apr 12.
We report the unprecedented sergeants and soldiers (S&S)-type remote control of one-handed helicity in copolymers of chiral/achiral biphenylylacetylenes bearing amphiphilic oligo(ethylene glycol) (OEG) side chains. A small amount of chiral binaphthyl residues (≤10 mol %) introduced at the terminal of the achiral OEG spacers as many as 80 bonds away from the polymer backbones induced a complete one-handed helix in water through preferential intramolecular encapsulation of the binaphthyl groups within a cavity of the copolymers. A fully one-handed helix can be induced virtually independent of the OEG spacer length and concentrations. At a specific spacer length, however, its helix-sense was inverted. The copolymers also form an excess one-handed helix in organic solvents in an OEG spacer-length dependent manner, yet far from the polymer backbones. We show the superiority of the present covalent-bond driven S&S-type remote helicity control over the corresponding noncovalent helicity induction approach.
我们报道了在手性/非手性联苯乙炔与两亲性低聚乙二醇（OEG）侧链的共聚物中，前所未有的“军士与士兵”（S&S）型单手螺旋远程控制。在手性OEG间隔基的末端引入少量萘基残基（≤10 mol %），这些间隔基距离聚合物主链多达80个键，通过在共聚物腔内优先分子内包封萘基，在水中诱导出完全的单手螺旋。几乎可以独立于OEG间隔基长度和浓度诱导出完全的单手螺旋。然而，在特定的间隔基长度下，其螺旋方向会反转。这些共聚物在有机溶剂中也以OEG间隔基长度依赖的方式形成过量的单手螺旋，但远离聚合物主链。我们展示了当前共价键驱动的S&S型远程螺旋控制相对于相应的非共价螺旋诱导方法的优越性。
