Polynuclear Copper(I) Complexes with Chelating Bis- and Tris-N-Heterocyclic Carbene Ligands: Catalytic Activity in Nitrene and Carbene Transfer Reactions

• Published in: European Journal of Organic Chemistry 2012-03, Vol.2012 (7), p.1367-1372
• Main Authors: Tubaro, Cristina, Biffis, Andrea, Gava, Riccardo, Scattolin, Elena, Volpe, Andrea, Basato, Marino, Díaz-Requejo, M. Mar, Perez, Pedro J.
• Format: Article
• Language: English
• Subjects: Aziridination; Carbenes; Catalysis; Catalysts: preparations and properties; Chemistry; Copper; Cyclopropanation; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Nitrenes; Nitrogen heterocycles; Organic chemistry; Preparations and properties; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201101480

Di‐ and trinuclear complexes of copper(I) bearing bis‐ or tris‐N‐heterocyclic carbene ligands have been prepared and evaluated as catalysts in nitrene transfer reactions from PhI=NTs to unsaturated and saturated substrates (olefin aziridination and C–H bond amidation) and carbene transfer reactions from diazo compounds to olefins. The complexes exhibited moderate‐to‐high catalytic activity in both processes. The tosylamidation of C–H bonds, previously unreported with a NHC‐containing copper catalyst, was promoted by the dinuclear complexes. Polynuclear oligo‐NHC–copper complexes catalyse the transfer of carbene or nitrene fragments to unsaturated and saturated substrates. The first example of the tosylamidation of C–H bonds with a catalyst containing the NHCCu core is described.