ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
Complete Submission.pdf (10.34 MB)

Mimicking Noncanonical Oxidations with Redox-Neutral Photocatalysis

preprint
submitted on 29.08.2019, 03:30 and posted on 30.08.2019, 14:29 by Zheng Huang, Jean-Philip Lumb
Noncanonical oxygenases are a family of Fe-containing enzymes that catalyze oxidative radical cyclizations. Despite creating key structural features that often define a natural product’s complexity, the mechanisms of these oxidations remain poorly understood and difficult to mimic. In this work, we show that noncanonical cyclizations from lignan biosynthesis can be recreated when presumed biosynthetic radicals are generated using photocatalysis. These conditions afford the ensuing electron rich radicals sufficient time to undergo challenging 5- or 11-membered ring formation that create the defining structural features of the highly oxidized lignans taiwankadsurins A, B and kadsuphilin N. By showing that these cyclizations can occur without enzymatic assistance, we provide a more general strategy for mimicking noncanonical transformations that should broaden their use in organic synthesis.

History

Email Address of Submitting Author

jean-philip.lumb@mcgill.ca

Institution

McGill University

Country

Canada

ORCID For Submitting Author

0000-0002-9283-1199

Declaration of Conflict of Interest

No Conflict of Interest

Exports

ChemRxiv

Exports