Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes

For the first time, the monoalkoxycarbonylation of easily available 1,3‐diynes to give synthetically useful conjugated enynes has been realized. Key to success was the design and utilization of the new ligand 2,2′‐bis(tert‐butyl(pyridin‐2‐yl)phosphanyl)‐1,1′‐binaphthalene (Neolephos), which permits the palladium‐catalyzed selective carbonylation under mild conditions, providing a general preparation of functionalized 1,3‐enynes in good‐to‐high yields with excellent chemoselectivities. Synthetic applications that showcase the possibilities of this novel methodology include an efficient one‐pot synthesis of 4‐aryl‐4H‐pyrans as well as the rapid construction of various heterocyclic, bicyclic, and polycyclic compounds.