Palladium-catalyzed carbon dioxide elimination-fixation reaction of 4-methoxycarbonyloxy-2-buten-1-ols.

A new type of palladium-catalyzed CO(2) recycling reaction using allylic carbonates is described. Reaction of trans-4-methoxycarbonyloxy-2-buten-1-ols in the presence of a palladium catalyst produces cyclic carbonates having a vinyl group via a CO(2) elimination-fixation process. A variety of allylic carbonates participate in the reaction giving cyclic carbonates with high efficiencies. Stereoselective construction of trans-cyclic carbonates is achieved by using nonsymmetric substrates. An enantiospecific reaction proceeds to give chiral cyclic carbonate when a chiral methyl-substituted substrate is subjected to the reaction conditions.