Li Zhi-Min, Tan Yingfei, Ma You-Ping, Cao Xiao-Ping, Chow Hak-Fun, Kuck Dietmar
State Key Laboratory of Applied Organic Chemistry and College of Chemistry & Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China.
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong.
J Org Chem. 2020 May 15;85(10):6478-6488. doi: 10.1021/acs.joc.0c00396. Epub 2020 Apr 24.
Starting from a hitherto unknown 2-aminotribenzotriquinacene, several 2-amino-3-X-substituted TBTQ derivatives, all bearing a single -difunctionalized indane wing, were synthesized as rigid and chiral building blocks for the potential construction of complex supramolecular architectures. Efficient access to two pairs of enantiomeric TBTQ derivatives, namely, the peripheral -nitroaniline (X = NO) and the related anthranilic acid (X = COH), was developed using chiral auxiliaries as the resolving reagents. The structure of the intermediate diastereomers was confirmed by H and C NMR spectroscopy, high-resolution mass spectroscopy (HRMS), and polarimetry. The absolute configuration of the optically active derivatives was confirmed by quantum chemical time-dependent density functional theory (TD-DFT) calculations of the theoretical electronic circular dichroism (ECD) spectra and by single-crystal X-ray structure analysis of a synthesis intermediate.
从一种迄今未知的2-氨基三苯并三喹吖嗪出发，合成了几种2-氨基-3-X-取代的TBTQ衍生物，它们都带有一个单双官能化茚满侧翼，作为构建复杂超分子结构的刚性手性结构单元。利用手性助剂作为拆分试剂，开发了有效合成两对对映体TBTQ衍生物的方法，即外围对硝基苯胺（X = NO）和相关邻氨基苯甲酸（X = COH）。通过氢谱和碳谱核磁共振波谱、高分辨质谱（HRMS）和旋光测定法确定了中间非对映异构体的结构。通过理论电子圆二色光谱（ECD）的量子化学含时密度泛函理论（TD-DFT）计算以及合成中间体的单晶X射线结构分析确定了光学活性衍生物的绝对构型。
