Synthesis and Application of New Compounds with Both Axial and Helical Chiralities

我们成功地合成了1，1 ′-联-2-萘酚（BINOL）低聚物（二聚体~八聚体），它们直接连接在（R）-BINOL的3，3 ′-位上，并且是纯的，总收率很高。 发现该二聚体作为手性亚砜的优良NMR位移试剂工作。相应的单钙配合物和低价双核钛配合物被发现作为一个手性双功能催化剂的硝基甲烷的迈克尔反应和频哪醇偶联反应，分别是有效的，其中诱导适合型反应是预期的。三聚体引起了有趣的独特的螺旋组装的水分子，从而导致形成手性单链水线。结果表明，BINOLs的动力学手性可受pH等外界刺激的控制，其紫外-可见光谱和圆二色光谱在五聚体上显示出不寻常的趋势，表明形成了单螺旋结构。

We succeeded in synthesizing 1,1'-bi-2-naphthol (BINOL) oligomers (dimer~octamer), which are directly connected at the 3,3'-positions of (R)-BINOL, in pure states and in good overall yields. The dimer was found to work as an excellent NMR shift reagent for chiral sulfoxides. The corresponding mono-calcium complex and low-valent dinuclear Ti-complex were found to work as a chiral bifunctional catalyst for the Michael reaction of nitromethane and to be effective for the pinacol coupling reaction, respectively, in which induced-fit-type reactions are anticipated. The trimer caused interestingly unique helical assembly of water molecules thus leading to the formation of chiral single strand water wire. It was found that the dynamic chirality of oligoBINOLs could be controlled by external stimuli such as pH. The UV-VIS and CD spectra of oligoBINOLs showed unusual trend on the pentamer indicating the formation of a unispiral structure.