Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
Institute of Medicinal Biotechnology, Chinese Academy of Medical Science, Beijing, 100050, China.
Nat Commun. 2022 Jul 29;13(1):4402. doi: 10.1038/s41467-022-31920-1.
The dearomative functionalization of aromatic compounds represents a fascinating but challenging transformation, as it typically needs to overcome a great kinetic barrier. Here, a catalyst-free dearomative rearrangement of o-nitrophenyl alkyne is successfully established by leveraging the remote oxygen transposition and a weak N-O bond acceleration. This reaction features high atom-, step- and redox-economy, which provides a divergent entry to a series of biologically important benzazepines and bridged polycycloalkanones. The reaction is proposed to proceed through a tandem oxygen transfer cyclization/(3 + 2) cycloaddition/(homo-)hetero-Claisen rearrangement reaction. The resulting polycyclic system is richly decorated with transformable functionalities, such as carbonyl, imine and diene, which enables diversity-oriented synthesis of alkaloid-like polycyclic framework.
芳香族化合物的去芳构化官能团化反应是一种引人入胜但极具挑战性的转化，因为它通常需要克服巨大的动力学障碍。在这里，通过利用远程氧迁移和弱 N-O 键加速，成功建立了无催化剂的邻硝基苯炔的去芳构化重排反应。该反应具有高原子经济性、高步骤经济性和高氧化还原经济性，为一系列具有重要生物意义的苯并氮杂卓和桥连多环烷酮提供了一个发散的入口。该反应被认为是通过串联氧转移环化/（3+2）环加成/（同/杂）Claisen 重排反应进行的。所得的多环体系富含可转化的官能团，如羰基、亚胺和二烯，这使得生物碱样多环骨架的多样性导向合成成为可能。
