title: Elevated catalytic activity of ruthenium(II)-porphyrin-catalyzed carbene/nitrene transfer and insertion reactions with N-heterocyclic carbene ligands.
abstract: 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.
authors: HKU Shenzhen Institute of Research and Innovation, Shenzhen 518053 (China); State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (China).
authors: Ka-Ho
authors: KH
authors: Chan
authors: Xiangguo
authors: X
authors: Guan
authors: Vanessa Kar-Yan
authors: VK
authors: Lo
authors: Chi-Ming
authors: CM
authors: Che
keywords: N-heterocyclic carbenes; carbene transfer; ligand effects; nitrene transfer; ruthenium