Chiral Derivatives of 2-Aminotribenzotriquinacene: Synthesis and Optical Resolution
Chiral Derivatives of 2-Aminotribenzotriquinacene: Synthesis and Optical Resolution
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2-氨基三苯并三醌的手性衍生物：合成和光学拆分
DOI：
10.1021/acs.joc.0c00396
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Dietmar Kuck
中科院分区：
文献类型：
--
作者：
Zhi-Min Li;Yingfei Tan;You-Ping Ma;Xiao-Ping Cao;Hak-Fun Chow;Dietmar Kuck
从一个未知的2-氨基-3-苯并三喹二烯出发，合成了几个2-氨基-3-X取代的TBTQ衍生物，它们都带有一个邻位取代的吲哚基翼，作为刚性和手性的构筑块，为潜在的构建复杂的超分子结构奠定了基础。以手性助剂为拆分剂，建立了两对对映体对映体TBTQ的有效拆分方法，即邻位邻硝基苯胺(X=NO2)和邻氨基苯甲酸(X=CO2H)。中间体的结构经~1H和~(13)C核磁共振谱、高分辨质谱学和旋光法确证。通过理论电子圆二色谱的量子化学含时密度泛函理论(TD-DFT)计算和合成中间体的单晶X射线结构分析，确定了光学活性衍生物的绝对构型。
Starting from a hitherto unknown 2-aminotribenzotriquinacene, several 2-amino-3-X-substituted TBTQ derivatives, all bearing a singleortho-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 peripheralortho-nitroaniline (X = NO2) and the related anthranilic acid (X = CO2H), was developed using chiral auxiliaries as the resolving reagents. The structure of the intermediate diastereomers was confirmed by1H and13C 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.