Hu Bingwei, Yan Wenxin, Jiang Peiyun, Jiang Ling, Yuan Xu, Lin Jun, Jiao Yinchun, Jin Yi
Key Laboratory of Medicinal for Natural Resource, Ministry of Education and Yunnan Province, School of Pharmacy, Yunnan University, 650091, Kunming, China.
School of Chemistry and Chemical Engineering, Key Laboratory of Theoretical Organic Chemistry and Functional Molecular, Ministry of Education, Hunan University of Science and Technology, 411201, Xiangtan, China.
Commun Chem. 2023 Jan 18;6(1):17. doi: 10.1038/s42004-022-00807-z.
Lawsones and indenopyrazoles are the prevalent structural motifs and building blocks in pharmaceuticals and bioactive molecules, but their synthesis has always remained challenging as no comprehensive protocol has been outlined to date. Herein, a metal-free, ring-expansion reaction of indantrione with diazomethanes, generated in situ from the N-tosylhydrazones, has been developed for the synthesis of lawsone and indenopyrazole derivatives in acetonitrile and alcohol solvents, respectively. It provides these valuable lawsone and pyrazole skeletons in good yields and high levels of diastereoselectivity from simple and readily available starting materials. DFT calculations were used to explore the mechanism in different solutions. The synthetic application example also showed the prospects of this method for the preparation of valuable compounds.
劳森酮和茚并吡唑是药物和生物活性分子中普遍存在的结构基序和构建单元，但它们的合成一直具有挑战性，因为迄今为止尚未概述全面的方法。在此，开发了一种茚三酮与由N-对甲苯磺酰腙原位生成的重氮甲烷的无金属扩环反应，分别在乙腈和醇溶剂中合成劳森酮和茚并吡唑衍生物。它从简单易得的起始原料中以良好的产率和高非对映选择性提供了这些有价值的劳森酮和吡唑骨架。使用密度泛函理论（DFT）计算来探索不同溶液中的反应机理。合成应用实例也展示了该方法在制备有价值化合物方面的前景。
