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Divergent synthesis of benzazepines and bridged polycycloalkanones via dearomative rearrangement.

ABSTRACT: 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.

SUBMITTER: Shi Q

PROVIDER: S-EPMC9338057 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Divergent synthesis of benzazepines and bridged polycycloalkanones via dearomative rearrangement.

Shi Qiu Q Liao Zhehui Z Liu Zhili Z Wen Jiajia J Li Chenguang C He Jiamin J Deng Jiazhen J Cen Shan S Cao Tongxiang T Zhou Jinming J Zhu Shifa S

Nature communications 20220729 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 ...[more]

PMID: 35906217

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