Dynamic‐to‐Static Planar Chirality Conversion in Pillar[5]arenes Regulated by Guest Solvents or Amplified by Crystallization
Dynamic‐to‐Static Planar Chirality Conversion in Pillar[5]arenes Regulated by Guest Solvents or Amplified by Crystallization
复制标题
由客体溶剂调节或通过结晶放大的柱[5]芳烃中的动态到静态平面手性转换
DOI：
10.1002/anie.202217971
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Ogoshi Tomoki
中科院分区：
文献类型：
--
作者：
Wada Keisuke;Suzuki Misaki;Kakuta Takahiro;Yamagishi Tada‐aki;Ohtani Shunsuke;Fa Shixin;Kato Kenichi;Akine Shigehisa;Ogoshi Tomoki
控制动态手性和记忆控制手性是很重要的。手性记忆主要是通过非共价相互作用来实现的。然而，在许多情况下，由非共价相互作用产生的手性通过改变溶剂和温度等条件而被消除。本研究通过共价键引入庞大基团，成功地将柱状[5]芳烃的动态平面手性转化为静态平面手性。在引入大体积基团之前，柱状[5]芳烃的两缘具有立体碳原子，是一对非对映体，因此表现出依赖于客体溶剂链长的平面手性反转。psandprforms由客体溶剂调节，通过引入大团来实现非对映记忆。此外，非对映体过剩被柱状[5]芳烃的结晶放大。随后引入的大块基团产生了具有优异的非对映体过量（95% de）的柱状[5]芳烃。
Controlling dynamic chirality and memorizing the controlled chirality are important. Chirality memory has mainly been achieved using noncovalent interactions. However, in many cases, the memorized chirality arising from noncovalent interactions is erased by changing the conditions such as the solvent and temperature. In this study, the dynamic planar chirality of pillar[5]arenes was successfully converted into static planar chirality by introducing bulky groups through covalent bonds. Before introducing the bulky groups, pillar[5]arene with stereogenic carbon atoms at both rims existed as a pair of diastereomers, and thus showed planar chiral inversion that was dependent on the chain length of the guest solvent. ThepSandpRforms, regulated by guest solvents, were both diastereomerically memorized by introducing bulky groups. Furthermore, the diastereomeric excess was amplified by crystallization of the pillar[5]arene. The subsequent introduction of bulky groups yielded pillar[5]arene with an excellent diastereomeric excess (95 %de).