Ru3(CO)12-Catalyzed Intermolecular Cyclocoupling of Ketones, Alkenes or Alkynes, and Carbon Monoxide. [2 + 2 + 1] Cycloaddition Strategy for the Synthesis of Functionalized γ-Butyrolactones

Abstract

The ruthenium-catalyzed intermolecular cyclocoupling of ketones (or aldehydes), alkenes (or alkynes), and CO, which leads to γ-butyrolactones, is described. The reaction represents the first example of the catalytic synthesis of heterocycles via an intermolecular carbonylative [2 + 2 + 1] cycloaddition. A wide variety of ketones, such as α-dicarbonyl compounds and N-heterocyclic ketones, can be used in this cycloaddition. The addition of phosphines is quite effective in reactions of α-dicarbonyl compounds. Of the phosphines examined, P(4-CF3C6H4)3 represents the additive of choice. Cyclic olefins, unpolarized terminal olefins, and internal alkynes can be successfully used in the synthesis of highly functionalized lactones. The introduction of a CF3 group to the aromatic portion of an aromatic keto ester accelerates the reaction of the keto ester with ethylene, while the introduction of a MeO group enhances the rate of the reaction of N-heterocyclic ketones with ethylene. The rate of the reaction increases...