Synthesis of Optically Active Polymer Ligands having Helix Structure

制备了具有多轴手性和多双齿位点的配体。通过2，4-戊二醇（PD）的栓系反应，合成了含3个萘基、2个2-萘酚和1个2，6-萘二醇的TERNOL。在常规条件下，PD栓系反应可以有效地收缩两个轴向手性。为了获得大量的光学活性萜醇，发展了一种新的光学拆分方法。还制备了具有四个萘啶基单元的高级类似物QUANOL。从（R）-BINOL出发，以良好的产率得到两种非对映体（R，R，R）-QUANOL和（R，S，R）-QUANOL。通过对它们的性质、溶解性、异构化、氧化还原和圆二色谱的研究，开发了新的不对称反应和光学拆分方法。BINOL的高级类似物作为具有多金属和氧化还原性质的复杂配体，具有促进立体选择性反应的潜力。

Ligands having multi axial chirality as well as multi bidentate sites were prepared. TERNOL having three naphythyl groups, two 2-naphthols and one 2,6-naphthodiol, was prepared by using 2,4-pentanediol (PD) tethered reaction. The PD tethered reaction was proved to be effective to contract two axial chiralities under the conventional conditions. To obtain a large quantity of optically active TERNOL, a new optical resolution method was developed. A higher analogue, QUANOL having four naphythyl units, was also prepared. From (R) -BINOL, two disastereomeric (R,R,R)-QUANOL and (R,S,R)-QUANOL were obtained in good yield. Their properties, solubility, isomerization, oxidation and reduction, and CD spectum were also disclosed.Through the research, I have developed new asymmetric reaciton and optical resolution method. The results also indicate that those higher analogs of BINOL have a potential to promote the stereoselective reaciton as sophisticated ligands having both multi metals and redox property.