Cu­(II)-mediated direct NH2 and NH alkyl aryl aminations and olefin aziridinations are described. These room-temperature, one-pot, environmentally friendly procedures replace costly Rh2 catalysts and, in some instances, display important differences with comparable Rh2- and Fe-supported reactions.

Direct C–H functionalization of aromatic compounds is a powerful tool for organic synthesis; however, differentiation among the ubiquitous and often chemically similar C–H bonds remains a significant challenge. Conflation with coordinating or directing groups incorporated into the intended substrate has helped address these limitations, although access to remote sites remains limited. Herein, we report an operationally simple and sustainable direct meta-selective H2N amination of benzylic and related aromatic picolinates under conditions mild enough to modify polyfunctional and late-stage molecules.

(±)-Asenapine, sold in the market as Saphris/Sycrest for the treatment of bipolar disorders, is synthesized in an optically pure form involving an Ireland-Claisen rearrangement as the key step. This approach allows access to all diastereomers.