Catalysis

Dearomative Photocatalytic Construction of Bridged 1,3-Diazepanes

Abstract

The construction of diverse sp3-rich skeletal ring systems is of importance to drug discovery programmes and natural product synthesis. Herein, we report the photocatalytic construction of 2,7-diazabicyclo[3.2.1]octanes (bridged 1,3-diazepanes) via a reductive diversion of the Minisci reaction. The fused tricyclic product is proposed to form via radical addition to the C4 position of 4-substituted quinoline substrates, with subsequent Hantzsch ester-promoted reduction to a dihydropyridine intermediate which undergoes in situ two-electron ring closure to form the bridged diazepane architecture. A wide scope of N-arylimine and quinoline derivatives was demonstrated and good efficiency was observed in the construction of sterically congested all-carbon quaternary centers. Computational and experimental mechanistic studies provide insights into the reaction mechanism and observed regioselectivity/diastereoselectivity.

Content

Thumbnail image of Dearomatization Chem Rxiv.pdf

Supplementary material

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Graphical Abstract
Thumbnail image of Dearomative Supporting information Chem Rxiv.pdf
Dearomative Supporting information Chem Rxiv
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crystallographic data
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xyz-methyl-phenyl