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
Key words
catalytic asymmetric synthesis - Friedel–Crafts reaction - iranium/irenium ions -
unsaturated bonds - electrophilic addition
