Rhodium-Catalyzed Enantioselective and Desymmetrizative Pauson–Khand Reaction: Access to Tricyclo[6.2.1.0^4,11]undecenes

Rhodium-catalyzed asymmetric desymmetrization Pauson–Khand reaction of C4-alkynyl-tethered cyclohexadienones has been developed as a novel strategy for access to fused 6–5–5 tricycles bearing three consecutive stereogenic centers. An array of chiral tricyclo­[6.2.1.0^4,11]­undecenes have been synthesized in high yields and enantioselectivities in a single step under mild conditions. This strategy employs readily accessible internal-olefin-containing 1,6-enynes, providing a potentially powerful tool for constructing chiral polycyclic scaffolds of complex molecules containing cyclopentenones and cyclohexenones.