Synthesis of Substituted 1,3‐Diene Synthetic Equivalents by a Ru‐Catalyzed Diyne Hydrative Cyclization

Catalyzed by [CpRu(CH3CN)3]PF6, the hydrative cyclization of dipropargylic sulfone substrates provides an effective way to synthesize highly functionalized substituted 3-sulfolenes. The amount of water is crucial for the reactivity of this cycloisomerization reaction. The scope and limitations of the Ru-catalyzed cycloisomerization are discussed. A marked ketone-directing effect was observed for the first time in ruthenium-catalyzed cyclizations. A plausible mechanism for the ketone-directed cycloisomerization is also rationalized. The utility of this method was demonstrated by both sulfur dioxide extrusion of the 3-sulfolenes to afford 1,3-dienes and subsequent inter- or intramolecular Diels-Alder reactions.