Catalytic Enantioselective Friedel–Crafts Reactions of Arenes Enabled by Iranium/Irenium-Ion-Triggered Electrophilic Functionalization

Abstract The catalytic asymmetric Friedel–Crafts reactions of (hetero)arenes represent a cornerstone in synthetic chemistry due to their ability to efficiently incorporate aromatic rings into complex molecular architectures. This account presents a comprehensive overview of recent advancements in the catalytic enantioselective Friedel–Crafts reactions of (hetero)arenes, with a particular focus on reactions that facilitate the introduction of aromatic rings into multiple C–C bonds via iranium/irenium-ion-triggered electrophilic processes. We examine in detail the strategies and methodologies employed to achieve stereoselective incorporation of (hetero)arenes into unsaturated C–C bonds, highlighting the construction of diverse structural scaffolds. Additionally, this account showcases the broad range of applications of this powerful transformation in organic synthesis. 1 Introduction 2 Catalytic Enantioselective Friedel–Crafts Reactions via Thiiranium/Thiirenium Ions 2.1 Arylthiiranium/Arylthiirenium-Ion-Triggered Catalytic Enantioselective Friedel–Crafts Reactions 2.2 Trifluoromethylthiiranium/Trifluoromethylthiirenium-Ion-Triggered Catalytic Enantioselective Friedel–Crafts Reactions 3 Catalytic Enantioselective Friedel–Crafts Reactions via Haliranium Ions 3.1 Chloriranium-Ion-Triggered Catalytic Enantioselective Friedel–Crafts Reactions 3.2 Bromiranium-Ion-Triggered Catalytic Enantioselective Friedel–Crafts Reactions 3.3 Iodiranium-Ion-Triggered Catalytic Asymmetric Oxidative Arylation of Alkenes 4 Conclusion and Outlook