Li Chunyang, Manick Anne-Doriane, Jean Marion, Albalat Muriel, Vanthuyne Nicolas, Dutasta Jean-Pierre, Bugaut Xavier, Chatelet Bastien, Martinez Alexandre
Aix Marseille Univ, CNRS, Centrale Marseille iSm2, 13284 Marseille, France.
Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, 46, Allée d'Italie, F-69364 Lyon, France.
J Org Chem. 2021 Nov 5;86(21):15055-15062. doi: 10.1021/acs.joc.1c01731. Epub 2021 Oct 1.
Two new hemicryptophanes combining a cyclotriveratrylene unit with either an aminotrisamide or a tris(2-aminoethyl)amine (tren) moiety have been synthesized. Although a conventional synthesis approach was used, the molecular cages obtained are devoid of the expected symmetry. NMR analyses and X-ray crystal structure determination showed that these hemicryptophanes exhibited symmetry due to the unusual arrangement of the substituents of the cyclotriveratrylene unit. This unprecedented arrangement is related to a change in the regioselectivity of the Friedel-Crafts reactions that led to the CTV cap. This constitutes an original approach to access enantiopure chiral molecular cages with low symmetry.
已经合成了两种新的半环番，它们将环三藜芦烃单元与氨基三酰胺或三（2-氨基乙基）胺（TREN）部分结合在一起。尽管使用了传统的合成方法，但得到的分子笼缺乏预期的对称性。核磁共振分析和X射线晶体结构测定表明，由于环三藜芦烃单元取代基的异常排列，这些半环番呈现出对称性。这种前所未有的排列与导致CTV帽的傅克反应区域选择性变化有关。这构成了一种获得低对称性对映纯手性分子笼的原始方法。
