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Dearomative Photocatalytic Construction of Bridged 1,3-Diazepanes

preprint
submitted on 11.11.2019 and posted on 20.11.2019 by Jamie Leitch, Tatiana Rogova, Fernanda Duarte, Darren J. Dixon
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.

Funding

EPSRC Centre for Doctoral Training in Synthesis for Biology and Medicine

Engineering and Physical Sciences Research Council

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History

Email Address of Submitting Author

jamie.leitch@chem.ox.ac.uk

Institution

University of Oxford

Country

United Kingdom

ORCID For Submitting Author

0000-0001-6997-184X

Declaration of Conflict of Interest

No conflict of interest

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in Angewandte Chemie

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