208176-50-5Relevant articles and documents
Copper-promoted N-cyclopropylation of anilines and amines by cyclopropylboronic acid
Benard, Sebastien,Neuville, Luc,Zhu, Jieping
supporting information; experimental part, p. 3393 - 3395 (2010/07/06)
Reaction of anilines, primary and secondary aliphatic amines with cyclopropylboronic acid in dichloroethane in the presence of Cu(OAc)2 (1 equiv.), 2,2′-bipyridine (1 equiv.) and sodium carbonate or sodium bicarbonate (2 equiv.) under air atmos
A mechanistic comparison between cytochrome P450- and chloroperoxidase-catalyzed N-dealkylation of N,N-dialkyl anilines
Bhakta, Mehul N.,Wimalasena, Kandatege
, p. 4801 - 4805 (2007/10/03)
Most peroxidases use histidine as an axial ligand for heme, while chloroperoxidase (CPO) uses a thiolate, which is similar to the ligand employed by cytochrome P450 (P450). Several studies have also shown that, unlike other peroxidases, CPO is capable of carrying out monooxygenation reactions in a similar manner to P450 in addition to typical peroxidase-like reactions. These observations have been attributed to the similarities of the active-site architecture of the two enzymes. Both enzymes have been shown to efficiently catalyze the oxidative N-dealkylation of amines. The similar magnitudes of the kinetic isotope effects determined for P 450- and CPO-catalyzed N-dealkylation of N,N-dimethylaniline have been used to propose that these reactions proceed through similar mechanisms. In this study, we have examined the mechanism of CPO-catalyzed N-dealkylation using a series of radical probes, 4-chloro-N-cyclopropyl-N-alkylanilines 1-3, which we have recently used in the mechanistic studies of P450, and compared the results with those of P450-catalyzed reactions. The results show that P450- and CPO-catalyzed reactions proceed through distinctly different mechanisms. As previously reported, while P 450-catalyzed reactions appear to proceed through a C α-hydrogen abstraction mechanism, CPO-catalyzed reactions proceed through a single electron/proton transfer (SET/H+) mechanism, similar to reactions catalyzed by Horseradish peroxidase (HRP). Thus, CPO may not be a good mechanistic model for P450-catalyzed N-dealkylations. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
Evidence for radical cations in linked mechanisms of N,N-Dialkyl aromatic amine nitration and nitrosative dealkylation
Loeppky, Richard N.,Singh, Sukhjeet P.,Elomari, Saleh,Hastings, Riley,Theiss, Thomas E.
, p. 5193 - 5202 (2007/10/03)
N,N,-Dialkyl aromatic amines react rapidly with nitrous acid to competitively produced a nitrosamine and a nitro compound. The mechanism of nitro compound formation involves a reaction of an amine radical cation with NO2, while the nitrosamine
