Hidden Reactivity of Barbituric and Meldrum’s Acids: Atom-Efficient Free Radical C–O Coupling with N-Hydroxy Compounds

The reactivity of CH-acidic and structurally related enol-containing heterocycles towards N-oxyl radicals was disclosed. Traditionally, these substrates were considered as reactants for ionic transformations. Highly selective and efficient N-oxyl radical mediated C–O coupling of substituted barbituric or Meldrum’s acids with N-hydroxy compounds (N-hydroxyimides, hydroxamic acids, oximes, and N-hydroxybenzotriazole) was achieved using inexpensive manganese-containing salts as oxidants. Metal-free C–O coupling was demonstrated using diacetyliminoxyl as both the oxidant (hydrogen atom acceptor) and the coupling partner.

A thermal decarboxylative Cloke–Wilson rearrangement of dispirocyclopropanes derived from para-quinone methides and bromo-Meldrum's acids: an approach to synthesize spirobutyrolactone para-dienones

An unprecedented approach to synthesize spirobutyrolactone para-dienones from para-quinone methides and bromo-Meldrum's acids has been developed.