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

Abstract A ruthenium‐catalyzed methodology for regioselective cycloisomerization and tandem Diels‐Alder reactions of 1,7‐enynes has been described, enabling the synthesis of diverse polycyclic heterocycles with four stereocenters. This stereoselective protocol demonstrates compatibility with various substituted enynes and alkenes, yielding products in 46–90% yield 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.