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ChemRxiv Masked N-centered radicals.pdf (442.77 kB)
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Exploiting Imine Photochemistry for Masked N-Centered Radical Reactivity

preprint
submitted on 27.11.2018 and posted on 28.11.2018 by Daryl Staveness, James L. Collins III, Rory C. McAtee, Corey Stephenson
This report details the development of a masked N-centered radical strategy that harvests the chemical potential of violet light to drive the conversion of cyclopropylimines to 1-aminonorbornanes. This process is initiated by the nitrogen-centered radical character of a photoexcited imine, facilitating the homolytic fragmentation of the cyclopropane ring followed by a radical cyclization sequence that forms two new C–C bonds en route to the norbornane core. Employing the excited state diyl of a Schiff base as a masked N‑centered radical is a unique mode of reactivity, the utility of which is amplified by the bathochromic shift into the visible spectrum imparted by the 4-nitrobenzimine. In addition to the intramolecular reactivity that generates 1‑aminonorbornanes, intermolecular formal [3+2] cycloadditions are also amenable to this strategy. This photochemical methodology operates in continuous flow, enhancing the potential to translate this approach beyond the academic sector.

Funding

NATIONAL INSTITUTES OF HEALTH (NIH)

United States Department of Health and Human Services

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AMERICAN CANCER SOCIETY

Centers for Disease Control and Prevention

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National Science Foundation

History

Email Address of Submitting Author

crjsteph@umich.edu

Institution

University of Michigan

Country

USA

ORCID For Submitting Author

0000-0002-2443-5514

Declaration of Conflict of Interest

No conflict of interest

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