Intramolecular Radical Amidooxygenation of Alkenes for the Construction of Pyrrolidinones.

An intramolecular 1,2-amidooxygenation of unactivated alkenes for the construction of the pyrrolidinone scaffold containing a masked 5-hydroxymethyl functionality is reported. γ,δ-Unsaturated N-aryloxyamides react with sodium 2,2,6,6-tetramethylpiperidin-1-olate (TEMPONa) to afford alkoxyaminated pyrrolidinones. The cascade proceeds through reductive amidyl radical generation with TEMPONa, 5-exo cyclization, and TEMPO trapping. No transition metal is required to perform these transformations, and complex (fused, bridged) pyrrolidinones are accessible in moderate to good yields. The product alkoxyamines are readily further converted into ketones and alcohols through either oxidation or reduction.