Ruthenium‐Catalyzed Regioselective Tandem Cycloisomerization/Diels‐Alder Reaction of 1,7‐Enynes

A ruthenium‐catalyzed methodology for regioselective cycloisomerization and tandem Diels‐Alder reactions of 1,7‐enynes has been described, enabling the versatile synthesis of diverse polycyclic heterocycles with four stereocenters. This stereoselective protocol demonstrates excellent compatibility with various substituted enynes and alkenes, yielding products in 46–90% yields while tolerating a wide range of functional groups, including esters, ketones, and halides. Notably, the reaction with naphthoquinones retains the moiety in the final product, which acts as essential core structures in various natural products and bioactive compounds.