College of Chemistry, Beijing Normal University, Beijing, 100875, China.
Key Laboratory of Bioorganic Phosphorous and Chemical Biology (MOE), Department of Chemistry, Tsinghua University, Beijing 100084, China.
Org Lett. 2023 Jul 14;25(27):5105-5110. doi: 10.1021/acs.orglett.3c01830. Epub 2023 Jun 29.
Despite their interesting stereochemistry and potential applications in (supramolecular) chemistry and chiroptical materials, inherently chiral macrocyclic compounds remain rare and are largely unexplored. We report herein a fragment coupling method to construct ABAC- and ABCD-type inherently chiral heteracalix[4]aromatics. The synthesis involves SAr CuI-catalyzed Ullmann coupling and aliphatic nucleophilic substitution reactions as key steps using readily available starting materials. Postmacrocyclization functionalization reactions enabled the production of amino-substituted and (benzo[])imidazole-2-(thi)one-bearing heteracalix[4]aromatics. Enantiopure ABCD-type macrocycles were obtained from resolution.
尽管它们具有有趣的立体化学和在（超分子）化学和手性光学材料中的潜在应用，但固有手性的大环化合物仍然很少见，并且在很大程度上尚未得到探索。我们在此报告了一种构建 ABAC-和 ABCD-型固有手性杂杯[4]芳烃的片段偶联方法。该合成涉及 SAr CuI 催化的 Ullmann 偶联和脂肪亲核取代反应作为关键步骤，使用易得的起始原料。后大环化官能化反应使氨基取代和（苯并[]咪唑-2-（硫）酮）取代的杂杯[4]芳烃得以生成。通过拆分获得了对映纯的 ABCD 型大环。
