Cobalt-Catalyzed Domino Transformations via Enantioselective C–H Activation/Nucleophilic [3+2] Annulation Towards Chiral Bridged Bicycles

Selective synthesis of chiral bridged (hetero)bicyclic scaffolds via asymmetric C–H activation constitutes substantial chal-lenges, due to the multiple reactivities of strained bicyclic structures. Herein, we develop the domino transformations through an unprecedent cobalt-catalyzed enantioselective C–H activation/nucleophilic [3+2] annulation with symmetrical bicyclic alkenes. The methods offer straightforward accesses to a wide range of chiral molecules bearing [2.2.1]-bridged bicy-clic cores with four and five consecutive stereocenters in a single step. Two elaborated salicyloxazoline (Salox) ligands were synthesized based on the rational design and mechanistic understanding. The well-defined chiral pockets generated from asymmetric coordination around trivalent cobalt catalyst direct the orientation of bicyclic alkenes, leading to the excellent enantioselectivity.