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PreprintCC BY-NC-NDChemRxiv

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

  • Osasere J. Osayawe1,2
  • Joshua D. Morgan1,2
  • Benjamin T. Melton1,2
  • Ethan P. Downing1,2
  • Jesus A. Botello1,2
  • Alexander Ramos1,2
  • Steven L. Castle1,2
  1. 1Department of Chemistry and Biochemistry
  2. 2Brigham Young University
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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.

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Cite

BibTeXRIS
BibTeX
@misc{osayawe2026intramolecular,
  title = {{Intramolecular N-Alkylation of O-Aryloximes Facilitates N–O Homolysis and Iminyl Radical Cyclization}},
  author = {Osasere J. Osayawe and Joshua D. Morgan and Benjamin T. Melton and Ethan P. Downing and Jesus A. Botello and Alexander Ramos and Steven L. Castle},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009361/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009361/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Intramolecular N-Alkylation of O-Aryloximes Facilitates N–O Homolysis and Iminyl Radical Cyclization
AU  - Osasere J. Osayawe
AU  - Joshua D. Morgan
AU  - Benjamin T. Melton
AU  - Ethan P. Downing
AU  - Jesus A. Botello
AU  - Alexander Ramos
AU  - Steven L. Castle
PY  - 2026
DA  - 2026/09/23
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009361/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009361/v1
AB  - 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.
ER  -