Work

Intramolecular N-Alkylation of O-Aryloximes Facilitates N–O Homolysis and Iminyl Radical Cyclization

Year: 2026

Type: preprint

Abstract: An attempt to improve a microwave-promoted iminyl radical cyclization cascade targeting the Securinega alkaloid virosinine A revealed that the process could be initiated at lower temperatures (66 °C versus 100 °C) under Finkelstein conditions. Mechanistic experiments and DFT calculations indicate that Finkelstein bromination or iodination facilitates intramolecular N-alkylation. This lowers the N–O BDE of the substrate and permits homolysis at lower temperatures than previously observed.

Source: ChemRxiv

DOI: 10.26434/chemrxiv.15009361/v1

Authors: Osasere J. Osayawe, Joshua D. Morgan, Benjamin T. Melton, Ethan P. Downing, Jesus A. Botello, Alexander Ramos, Steven L. Castle

Institution: Brigham Young University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, Brigham Young University, Division of Chemistry

Awards: G9000075419, No Catalyst Required: New Thermally-Promoted Transformations of Iminyl Radicals for the Synthesis of Complex Molecules

OpenAlex ID: W7214123405

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