Highly selective carboxylative cyclization of allenylmethylamines with carbon dioxide using N-heterocyclic carbene-silver(I) catalysts.

Abstract

Silver(I) carboxylate complexes promote the carboxylative cyclization of allenylmethylamines to afford 5-alkenyl-1,3-oxazolidin-2-ones in 2-propanol. The use of an N-heterocyclic carbene ligand (IPr) under pressurized CO2 is effective in suppressing the intramolecular hydroamination that leads to 2,5-dihydropyrroles. The mechanism involving a nucleophilic attack of the carbamate of the allene moiety and a subsequent protonation was realized on the basis of experimental and theoretical results involving a model intermediate, the alkenylgold(I) complex, which was synthesized from Au(OH)(IPr) and 1-methylamino-2,3-butadiene.