Guan Chun-Yan, Zou Shuai, Luo Can, Li Zhen-Yu, Huang Mingjie, Huang Lihua, Xiao Xiao, Wei Donghui, Wang Min-Can, Mei Guang-Jian
Henan Key Laboratory of Chemical Biology and Organic Chemistry, College of Chemistry, Zhengzhou University, Zhengzhou, China.
Pingyuan Laboratory (Zhengzhou University), Zhengzhou, China.
Nat Commun. 2024 May 29;15(1):4580. doi: 10.1038/s41467-024-48947-1.
Chirality constitutes an inherent attribute of nature. The catalytic asymmetric synthesis of molecules with central, axial, and helical chirality is a topic of intense interest and is becoming a mature field of research. However, due to the difficulty in synthesis and the lack of a prototype, less attention has been given to planar chirality arising from the destruction of symmetry on a single planar ring. Herein, we report the catalytic asymmetric synthesis of planar-chiral dianthranilides, a unique class of tub-shaped eight-membered cyclic dilactams. This protocol is enabled by cinchona alkaloid-catalyzed (dynamic) kinetic resolution. Under mild conditions, various C- or C-symmetric planar-chiral dianthranilides have been readily prepared in high yields with excellent enantioselectivity. These dianthranilides can serve as an addition to the family of planar-chiral molecules. Its synthetic value has been demonstrated by kinetic resolution of racemic amines via acyl transfer, enantiodivergent synthesis of the natural product eupolyphagin, and preliminary antitumor activity studies.
手性是自然界的一种固有属性。具有中心手性、轴手性和螺旋手性分子的催化不对称合成是一个备受关注的课题，正成为一个成熟的研究领域。然而，由于合成困难且缺乏原型，由单个平面环上对称性破坏产生的平面手性受到的关注较少。在此，我们报道了平面手性二蒽酰胺的催化不对称合成，这是一类独特的管状八元环双内酰胺。该方法通过金鸡纳生物碱催化的（动态）动力学拆分实现。在温和条件下，各种C-或C-对称的平面手性二蒽酰胺已能以高产率和优异的对映选择性轻松制备。这些二蒽酰胺可作为平面手性分子家族的补充。通过外消旋胺的酰基转移动力学拆分、天然产物土贝母苷元的对映发散合成以及初步的抗肿瘤活性研究，已证明了其合成价值。
