Ketone Oximes as NO2 Radical Precursors for Regioselective Iodo–Nitrosylative Cyclization of Unactivated 1,6-Enynes
Mohana Reddy Mutra, T. L. Chandana, Yu-Syuan Chu, Chien-Hung Li, Jeh-Jeng Wang
TL;DR
A new chemical method uses ketone oximes to create complex molecules from simple starting materials without metals or catalysts.
Contribution
Introduces oximes as a new, stable source of NO2 radicals for selective chemical reactions.
Findings
The method enables a metal-free cascade reaction of unactivated 1,6-enynes.
It produces 4-(iodo(phenyl)methylene)-3-(nitromethyl)-1-tosylpyrrolidines through a selective sequence.
Oximes are shown to be effective and stable NO2-radical donors for such transformations.
Abstract
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 (NO2) radical source under I2/aqueous TBHP conditions. This transformation proceeds through a chemo- and regioselective sequence involving NO2· 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 NO2-radical donors for cascade transformations.
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Taxonomy
TopicsRadical Photochemical Reactions · Catalytic C–H Functionalization Methods · Catalytic Cross-Coupling Reactions