Solid-phase supported nitrosocarbonyl intermediates: Old scope and new limitations in the organic synthesis

Nitrosocarbonyl intermediates on solid polystyrenic support are generated at room temperature by the mild oxidation of resin-bound stable nitrile oxides. They undergo one-pot ene reactions with tetramethyl- and trimethyl-ethylene and other highly substituted olefins. Less substituted ethylenes as well as cyclohexene and cyclopentene are heavily disfavoured and nitrosocarbonyls on solid phase undergo fast dimerization and/or decomposition pathways. These outcome strongly limit the SP applications in organic synthesis, although applicable to structurally specific N-alkenyl hydroxamic acids.