Redox‐Triggered CC Coupling of Diols and Alkynes: Synthesis of β,γ‐Unsaturated α‐Hydroxyketones and Furans by Ruthenium‐Catalyzed Hydrohydroxyalkylation

Direct ruthenium‐catalyzed C? C coupling of alkynes and vicinal diols to form β,γ‐unsaturated ketones occurs with complete levels of regioselectivity and good to complete control over the alkene geometry. Exposure of the reaction products to substoichiometric quantities of p‐toluenesulfonic acid induces cyclodehydration to form tetrasubstituted furans. These alkyne‐diol hydrohydroxyalkylations contribute to a growing body of merged redox‐construction events that bypass the use of premetalated reagents and, hence, stoichiometric quantities of metallic by‐products.