Elevated Catalytic Activity of Ruthenium(II)–Porphyrin‐Catalyzed Carbene/Nitrene Transfer and Insertion Reactions with N‐Heterocyclic Carbene Ligands

Bis(NHC)ruthenium(II)-porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans M=CRR'/M=NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C-H, N-H, S-H, and O-H insertion, alkene aziridination, and nitrene C-H insertion with turnover frequencies up to 1950 min(-1). The use of chiral [Ru(D4-Por)(BIMe)2] (1 g) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98% ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal-carbene reaction intermediate.