Palladium-Catalyzed Carbamate-Directed Regioselective Halogenation: A Route to Halogenated Anilines

This study describes an efficient method for ortho-selective halogenation of <i>N</i>-arylcarbamates under mild conditions for the first time. Although being weakly coordinating, <i>N</i>-arylcarbamates act very well as a removable directing group for activation of C–H bonds. The developed procedure results in extremely valuable halogenated <i>N</i>-arylcarbmates that can further be hydrolyzed to halogenated anilines. The obtained reaction conditions showed broad scope and wide functional group tolerance. All the products were formed in good yields with extremely high selectivity

Regioselective Diversification of 2,1-Borazaronaphthalenes: Unlocking Isosteric Space via C–H Activation

Methods for the regioselective C–H borylation and subsequent cross-coupling of the 2,1-borazaronaphthalene core are reported. Azaborines are dependent on B–N/CC isosterism when employed in strategies for developing diverse heterocyclic scaffolds. Although 2,1-borazaronaphthalene is closely related to naphthalene in terms of structure, the argument is made that the former has electronic similarities to indole. Based on that premise, iridium-mediated C–H activation has enabled facile installation of a versatile, nucleophilic coupling handle at a previously inaccessible site of 2,1-borazaronaphthalenes. A variety of substituted 2,1-borazaronaphthalene cores can be successfully borylated and further cross-coupled in a facile manner to yield diverse C(8)-substituted 2,1-borazaronaphthalenes