21163-79-1Relevant articles and documents
Targeting peptides with an iron-based oxidant: Cleavage of the amino acid backbone and oxidation of side chains
Ekkati, Anil R.,Kodanko, Jeremy J.
, p. 12390 - 12391 (2008/03/30)
The oxidation of protected amino acids using an iron-based oxidant is described. Substrates of the general formula Ac-X-NHtBu, where X = Gly (1), Ala (2), Val (3), Phe (4), Tyr (5), Trp (6), and Met (7) were constructed to model individual amino acid residues within a polypeptide chain. Oxidation of 1 by the iron catalyst [FeII(N4Py)(MeCN)](ClO4)2 (8) and KHSO5 leads to scission of the amino acid backbone and produces N-acetylformamide as the major product. Decomposition of the iron-based oxidant [FeIV(O)(N4Py)]2+, derived from 8, is slower in the presence of 2,2-d2-1 (96% D) than with 1, giving a kinetic isotope effect of 4.8, which is consistent with [FeIV(O)(N4Py)]2+ cleaving an α-CH bond of 1. Aliphatic amino acid substrates 2 and 3 do not react with [FeIV(O)(N4Py)]2+ under the same conditions used with 1. With substrates 4-7 oxidation of the amino acid side chain is observed. Decomposition of [FeIV(O)(N4Py)]2+ upon treatment with 10 equiv of 1 and 4-7 revealed that 5 is the most reactive toward the FeIVO species. Pseudo-first-order rate constants of 17.0(5) × 10-3, 3.15(8) × 10-3 and 5.8(2) × 10-5 s-1 were obtained for decomposition of [FeIV(O)(N4Py)]2+ ([Fe] = 1 mM, 1:1 H2O/MeCN) by 6, 7, and 1, respectively. Copyright
Electrochemical Reduction of N-(2,2,2-Trichloroethyl)acetamides
Casadei, Maria Antonietta,Moracci, Franco Micheletti,Occhialini, Donatella,Inesi, Achille
, p. 1887 - 1892 (2007/10/02)
The electrochemical reduction, at mercury cathode, of dimethylformamide solutions, containing Et4NClO4 as supporting electrolyte, of N-(2,2,2-trichloroethyl)acetamides (1a-f), with or without added water as proton source, has been investigated.In all cases, the nature and yield of the products from macroscale electrolyses as well as voltammetric data point to the formation of an intermediate carbanion, which undergoes β-eliminitation, or α-elimination, or acid-base reaction depending on the nature of the substituent on the carbon α to nitrogen and the medium.The formation of (2a) from the electrolysis of (1a-b) in the presence of H2O has been ascribed to nucleophilic substitution of the first-formed dehalogenated product by dimethylamine.The latter arises from decomposition of the solvent promoted by ions released in the follow-up reactions of the carbanion.
