Chemistry of Optically Active Helicenes

我们开发了一种光学纯螺旋烯的复合合成方法，1,12 -二甲基苯并[c]菲- 5,8 -二羧酸，这使我们能够对分子中的螺旋度进行化学研究。本文研究了含螺旋烯的大环化合物的合成及其性质。采用双向合成法合成了含有1 ~ 10个螺旋烯单元的环酰胺。对它们的结构进行了光谱比较，在小于五聚体的化合物中观察到“环效应”。较大的化合物被证明具有柔性结构。合成了含有3 ~ 6个螺旋烯的环炔。发现三聚体在有机溶剂中自聚集。该化合物仅形成二聚体，在检测的浓度范围内未观察到较高的聚集。螺旋烯部分的手性对聚合行为起重要作用。采用一锅法合成了含三螺旋烯环酸酐和含四螺旋烯环酸酐。研究了螺旋二羧酸酯的区域选择性多硝化反应，并开发了在对称位置进行功能化的方法。研究了四硝基螺旋烯与芘的电荷转移络合反应。比较了旋光螺旋烯与外消旋衍生物的晶体结构。用缺电子螺旋烯和富电子螺旋烯研究了ct络合中的手性识别。相同构型的螺旋螺旋形成更稳定的络合物。

We developed a multigram synthesis of an optically pure helicene, 1, 12-dimethylbenzo [c] phenanthrene-5, 8-dicarboxylic acid, which enabled us to conduct studies on the chemistry of helicity in the molecules. The present study deals with the synthesis and properties of macrocyclic compounds containg the helicene.1. Cycloamides containing one to ten helicene units were synthesized by a two-directional method. Their structures were compared spectroscopically, and "ring effect" was observed in the compounds smaller than the pentamer. The larger compounds turned out to possess flexible structures.2. Cycloalkynes contining three to six helicenes were synthesized. The trimer was found to self-aggregate in organic solvents. The compound formed only dimer, and higher-aggregation was not observed in the concentration range examined. The chirality at the helicene moiety played an important role in the aggregation behaviors.3. Cyclic anhydrides containing three and four helicenes were synthesized by a one-pot method.4. Regioselective polynitration of the helicenedicarboxylate was examined, and methods to functionalize at the symmetrical positions were developed.5. The charge-transfer (CT) complexation of a tetranitrohelicene with pyrene was examined. The crystal structure of the optically active helicene was compared with the racemic derivative. Chiral recognition in the CT-complexation was also studied using the electron-deficient helicene and an elecron-rich helicene. The same configuration of the helicenes formed more stable complex.