Ketone Oximes as NO 2 Radical Precursors for Regioselective Iodo–Nitrosylative Cyclization of Unactivated 1,6-Enynes
Abstract
High Resolution Image Download MS PowerPoint Slide A metal-free three-component radical cascade cyclization of unactivated 1,6-enynes has been developed using 1-phenylethan-1-one oxime as a novel in situ nitrogen dioxide (NO 2 ) radical source under I 2 /aqueous TBHP conditions. This transformation proceeds through a chemo- and regioselective sequence involving NO 2 · addition to the terminal alkene, 5-exo-dig cyclization onto the alkyne, and iodine trapping of the resulting carbon-centered radical, yielding 4-(iodo(phenyl)methylene)-3-(nitromethyl)-1-tosylpyrrolidines. This strategy avoids transition metals, photocatalysts, or prefunctionalized nitrogen reagents and highlights the previously unexplored potential of oximes as bench-stable NO 2 -radical donors for cascade transformations.
Fields of Study & Subjects
Radical Photochemical Reactions
Catalytic C–H Functionalization Methods
Catalytic Cross-Coupling Reactions
Publication details
- Journal / source
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Volume
- 91
- Issue
- 2
- Pages
- 966–972
- Publication date
- 2 January 2026
- Language
- EN