doi:10.1021/acscatal.2c05895engTarifa, L.Río, M. P. delAsensio, L.López, J. A.Ciriano, M. A.Geer, A. M.Tejel, C.Iridium-Catalyzed Regio- and Diastereoselective Synthesis of C-Substituted PiperazinesART-2023-132904Piperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies are mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines based on an uncommon head-to-head coupling of easily prepared imines. This 100% atom-economic process allows the selective formation of a sole diastereoisomer, a broad substrate scope, and a good functional group tolerance employing a bench-stable iridium catalyst under mild reaction conditions. Key to the success is the addition of N-oxides to the reaction mixture, as they notably enhance the catalytic activity and selectivity.2023http://zaguan.unizar.es/record/12444310.1021/acscatal.2c05895http://zaguan.unizar.es/record/124443oai:zaguan.unizar.es:124443info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00info:eu-repo/grantAgreement/ES/DGA/E50-20Dinfo:eu-repo/grantAgreement/ES/MICINN/IJC-2018-035231-IACS CATALYSIS 13, 5 (2023), 3148-3152byhttp://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccess