A novel palladium(0)-catalyzed dearomative cyclization reaction of bromophenols with (1,n)-diynes has been developed for building two new types of tricyclic architectures containing a quaternary carbon center. This method employs inexpensive bromophenols, and easily accessible tethered diynes. It exhibits a broad substrate scope and tolerates various functional groups. Preliminary results with commercially available chiral ligands indicate that enantioselective variants are feasible for both cyclization processes.

A novel palladium(0)-catalyzed dearomative cyclization reaction of bromophenols with (1,n)-diynes has been developed for building two new types of tricyclic architectures containing a quaternary carbon center. This method employs inexpensive bromophenols, and easily accessible tethered diynes. It exhibits a broad substrate scope and tolerates various functional groups. Preliminary results with commercially available chiral ligands indicate that enantioselective variants are feasible for both cyclization processes.

A novel palladium(II)-catalyzed [5+2] oxidative annulation of readily available o-arylanilines with alkynes has been developed for building a seven-membered N-heterocyclic architecture containing a biaryl linkage. This method is applicable to a wide range of unprotected o-arylanilines and internal alkynes, and results in the chemoselective preparation of imine-containing dibenzo[b,d]azepines in high yields with excellent diastereoselectivity with respect to the two types of stereogenic elements.

A novel palladium(II)-catalyzed [5+2] oxidative annulation of readily available o-arylanilines with alkynes has been developed for building a seven-membered N-heterocyclic architecture containing a biaryl linkage. This method is applicable to a wide range of unprotected o-arylanilines and internal alkynes, and results in the chemoselective preparation of imine-containing dibenzo[b,d]azepines in high yields with excellent diastereoselectivity with respect to the two types of stereogenic elements.

Catalytic asymmetric aminative dearomatization of 1-substituted 2-naphthols was successfully implemented with electrophilic azodicarboxylates under the catalysis of chiral Sc^III/pybox complexes. This intermolecular reaction represents a hitherto unknown enantioselective CN bond-forming process through direct dearomatization of phenolic compounds to generate chiral nitrogen-containing quaternary carbon stereocenters.

Catalytic asymmetric aminative dearomatization of 1-substituted 2-naphthols was successfully implemented with electrophilic azodicarboxylates under the catalysis of chiral Sc^III/pybox complexes. This intermolecular reaction represents a hitherto unknown enantioselective CN bond-forming process through direct dearomatization of phenolic compounds to generate chiral nitrogen-containing quaternary carbon stereocenters.