Indane-Based Chiral Aryl Chalcogenide Catalysts: Development and Applications in Asymmetric Electrophilic Reactions

• DOI: 10.1021/acs.accounts.2c00201
• Publication Date: 2022-08-25T19:13:02Z
• Authors: Lihao Liao; Xiaodan Zhao
• Keywords: Indane; Desymmetrization

ConspectusAsymmetric electrophilic reactions provide an ideal method for the construction of chiral molecules by incorporating one or more functional groups into parent substrates under mild conditions. However, due to issues reactivities species and possible racemization intermediates as well restriction scaffolds catalysts, many limitations remain in this field, such narrow scopes electrophiles limited types nucleophiles reactions. To overcome synthesis diversified molecules, we developed a series indane-based amino aryl chalcogenide catalysts. These catalysts are easily prepared based on privileged indane scaffold. They can appropriate H-bonding effect varying protecting offer proper Lewis basicity steric hindrance adjusting different substituents motifs. features allow them meet requirements reactivity environment Notably, they have been successfully applied various asymmetric alkenes, alkynes, arenes, expanding field reactions.Using these realized enantioselective CF3S-lactonization olefinic carboxylic acids, CF3S-aminocyclization sulfonamides, desymmetrizing CF3S-carbocyclization gem-diaryl-tethered CF3S-oxycyclization N-allylamides, intermolecular trifluoromethylthiolating difunctionalization allylic C–H trifluoromethylthiolation trisubstituted formally CF3S-oxyfunctionalization aliphatic internal azidothiolation, oxythiolation, thioarylation N-allyl chlorocarbocyclization aryl-tethered diolefins, Friedel–Crafts-type chlorination anilides, dearomatization 1-naphthanilides. Additionally, carbothiolation alkynes construct enantiopure carbon chirality center-containing axially sulfide vinyl arenes aromatic halogenation produce P-chirogenic compounds be accomplished. In reactions, bifunctional binding mode is proposed catalytic cycles, which acid-derived anion-binding interaction might exist account high enantioselectivities reactions.In Account, demonstrate our achievements share thoughts catalyst design, understanding perspectives chalcogenide-catalyzed We hope that experience will promote design development other novel organocatalysts new challenging