Takase Ko, Noguchi Keiichi, Nakano Koji
J Org Chem. 2018 Dec 21;83(24):15057-15065. doi: 10.1021/acs.joc.8b02301. Epub 2018 Dec 11.
Spiro polycyclic aromatic compounds have been known as rigid chiral scaffolds. In order to extend their applications, an efficient preparation route to enantiopure derivatives is highly required. Here, we design 10,10'-spirobi[indeno[1,2- b][1]benzothiophene]-7,7'-diol to achieve efficient optical resolution. The compound was successfully synthesized and resolved by chiral HPLC on a semipreparative scale. The absolute configuration of its enantiopure isomer was determined through single-crystal X-ray structure analysis of its derivative. The compound was also transformed into its derivatives with donor-acceptor (D-A) type systems. The obtained chiral D-A type molecules exhibited remarkable solvent-dependence fluorescence and were found to be solvent-sensitive circularly polarized luminescent materials. These results clearly demonstrated the utility of 10,10'-spirobi[indeno[1,2- b][1]benzothiophene]-7,7'-diol as a versatile building block for chiral spiro polycyclic aromatic compounds.
螺环多环芳烃已被认为是刚性手性骨架。为了扩展其应用，迫切需要一种高效制备对映体纯衍生物的路线。在此，我们设计了10,10'-螺二茚并[1,2-b][1]苯并噻吩]-7,7'-二醇以实现高效的光学拆分。该化合物通过半制备规模的手性高效液相色谱成功合成并拆分。通过其衍生物的单晶X射线结构分析确定了其对映体纯异构体的绝对构型。该化合物还被转化为具有供体-受体（D-A）型体系的衍生物。所获得的手性D-A型分子表现出显著的溶剂依赖性荧光，并被发现是溶剂敏感的圆偏振发光材料。这些结果清楚地证明了10,10'-螺二茚并[1,2-b][1]苯并噻吩]-7,7'-二醇作为手性螺环多环芳烃通用构建块的实用性。
