Highly Enantioselective Formal Synthesis of (+)‐Treprostinil Enabled by Rhodium‐Catalyzed Enyne Cycloisomerization

Comprehensive Summary Herein, a highly enantioselective formal synthesis of (+)‐Treprostinil via the interphenylene prostaglandin E 1 scaffold was described. The chiral multi‐substituted cyclopentanone was constructed via a [Rh(Duanphos)SbF 6 ‐catalyzed asymmetric enyne cycloisomerization and a copper hydride‐mediated conjugate reduction. In addition, a new type of interphenylene prostaglandin scaffold was obtained via a formal Alder‐ene reaction in high yield with excellent chemoselectivity.