Manganese-catalyzed aziridination of olefins with chloramine-T in water and buffered aqueous solutions

(Salen)Mn(III)-Catalyzed Enantioselective Intramolecular Haloamination of Alkenes through Chiral Aziridinium Ion Ring-Opening Sequence

“…Moreover, manganese-complex 8a, which was generated from 7a, was detected by high-resolution mass spectrometry (Scheme 4, (1c)). 16 This observation suggests that chiral (Salen)Mn(III) complex preferentially interact with amino group of substrate to furnish Mn−N intermediate in this reaction. A radical trapping experiment with TEMPO and 5a revealed that the reaction was completely inhibited and 87% of 5a was recovered.…”

“…These results implied that 5a was an intermediate of the reaction, and the chiral (Salen)­Mn­(III) complex would not interact with olefins through epoxidation reactions under the reaction conditions. Moreover, manganese-complex 8a , which was generated from 7a , was detected by high-resolution mass spectrometry (Scheme , (1c)) . This observation suggests that chiral (Salen)­Mn­(III) complex preferentially interact with amino group of substrate to furnish Mn–N intermediate in this reaction.…”

“…The aminium radical-cation (g = 2.0028) and triplet Mn ligand radical was observed for the spectrum of EPR, 18 which was consistent with the hypothesis that Mn−N intermediates would exist in triplet electronic ground states. At last, aziridine product 9 was assessed with styrene and p-toluenesulfonamide, 16 which revealed that the reaction of (Salen)Mn(III)-catalyzed enantioselective intramolecular haloamination of alkenes could generate a chiral aziridines intermediate.…”

Three water-soluble copper(ii) N-heterocyclic carbene complexes: toward copper-catalyzed ketone reduction under sustainable conditions

“…This data suggests that ligand hydrophobicity does not correlate to DNA affinity as demonstrated for other DNA hybrid systems. 36,37,60 Further changes to the ligand architecture are likely required in these NHC ligands to improve the DNA binding thermodynamics required substantial chiral selectivity.…”

Recent advances in the accessibility, synthetic utility, and biological applications of aziridines

“…Zirconium has also been employed as a catalyst for the synthesis of aziridine derivatives. Moura-Letts and co-workers described the aziridination of alkenes ( 41 ) by using chloramine T 17 ( 52 ) as the quantitative source of nitrogen (Scheme 9). Supported by kinetics and model reaction studies, the authors propose that the reaction mechanism involves the formation of a zirconooxaziridine complex ( 53 ) as the active catalyst.…”