68820-12-2Relevant articles and documents
Manganese-catalyzed aziridination of olefins with chloramine-T in water and buffered aqueous solutions
Wolgemuth, Daniel K.,Elmore, Sydnee D.,Cope, James D.,Sheridan, Patrick E.,Stokes, Sean L.,Emerson, Joseph P.
, (2021/01/04)
A water-soluble, manganese-porphyrin complex was used to catalytically generate aziridines from olefins in moderate to good yields (up to 93%) upon optimization at room temperature and in aqueous media. Reactions using chloramine-T at slightly acidic to n
A Dicopper Nitrenoid by Oxidation of a CuICuICore: Synthesis, Electronic Structure, and Reactivity
Desnoyer, Addison N.,Nicolay, Amélie,Ziegler, Micah S.,Lakshmi,Cundari, Thomas R.,Tilley, T. Don
supporting information, p. 7135 - 7143 (2021/05/31)
A dicopper nitrenoid complex was prepared by formal oxidative addition of the nitrenoid fragment to a dicopper(I) center by reaction with the iminoiodinane PhINTs (Ts = tosylate). This nitrenoid complex, (DPFN)Cu2(μ-NTs)[NTf2]2 (DPFN = 2,7-bis(fluorodi(2-pyridyl)methyl)-1,8-naphthyridine), is a powerful H atom abstractor that reacts with a range of strong C-H bonds to form a mixed-valence Cu(I)/Cu(II) μ-NHTs amido complex in the first example of a clean H atom transfer to a dicopper nitrenoid core. In line with this reactivity, DFT calculations reveal that the nitrenoid is best described as an iminyl (NR radical anion) complex. The nitrenoid was trapped by the addition of water to form a mixed-donor hydroxo/amido dicopper(II) complex, which was independently obtained by reaction of a Cu2(μ-OH)2 complex with an amine through a protonolysis pathway. This mixed-donor complex is an analogue for the proposed intermediate in copper-catalyzed Chan-Evans-Lam coupling, which proceeds via C-X (X = N or O) bond formation. Treatment of the dicopper(II) mixed donor complex with MgPh2(THF)2 resulted in generation of a mixture that includes both phenol and a previously reported dicopper(I) bridging phenyl complex, illustrating that both reduction of dicopper(II) to dicopper(I) and concomitant C-X bond formation are feasible.
Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents
Kalra, Anshika,Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Ai, Lin,Sanakis, Yiannis,Raptopoulos, Grigorios,Mohapatra, Sudip,Choudhury, Amitava,Sun, Zhicheng,Cundari, Thomas R.,Stavropoulos, Pericles
, p. 1974 - 1996 (2021/06/28)
Recent research has highlighted the key role played by the electron affinity of the active metal-nitrene/imido oxidant as the driving force in nitrene additions to olefins to afford valuable aziridines. The present work showcases a library of Co(II) reage