Diversity-oriented synthesis

The dearomative functionalization of aromatic compounds represents a challenging transformation, as it typically needs to overcome a great kinetic barrier. Here, the authors disclose a weak-bond-accelerated, catalyst-free dearomative [3,3]-rearrangement of o-nitrophenyl alkyne for the divergent synthesis of benzazepines and bridged polycycloalkanones via remote oxygen transposition.

Given their low cost and diverse nature, coupling of amine and carboxylic acid building blocks provides an opportunity to expand the accessible chemical space. Here, a copper-catalyzed deaminative esterification of aryl amines with carboxylic acids is developed and its use in library synthesis with high-throughput experimentation is demonstrated.

The α-arylation of amides via aryl migration has attracted considerable interest in recent years. Here, the authors report a method for the preparation of bulky α-quaternary amides via a polar-radical crossover enolate oxidation-aryl migration cascade.

The Mannich reaction is a three-component reaction for preparing alkylamines, but the nucleophilic components rely on C(sp²)−H and activated C(sp³)−H bonds. Here, the authors report an unprecedented multicomponent double Mannich alkylamination for both C(sp²)−H and unactivated benzylic C(sp³)−H bonds.