1730-97-8Relevant articles and documents
Mn(III) oxidation of peptides: A mechanistic investigation of kinetic variations in hydrophobic-induced oxidation of tetrapeptides of elastin sequences
Srinivasa,Abiraj,Baba, A. Ramesha,Gowda, D. Channe
, p. 115 - 123 (2008/02/03)
Four tetrapeptide analogues of elastin sequences, glycyl-glycyl-alanyl- proline (GGAP), glycyl-glycyl-valyl-proline (GGVP), glycyl-glycyl-isoleucyl- proline (GGIP), and glycyl-glycyl-phenylalanyl-proline (GGFP) were synthesized, based on their increasing order of hydrophobicity, by a classical solution phase method and were characterized. These tetrapeptides (TETPs) were oxidized using Mn(OAc)3 in 25% acetic acid at 298 K, and the kinetics of the reaction was monitored spectrophotometrically at λmax == 400 nm. A first-order dependence of rate on each of [Mn(OAc)3], [OAc -], and substrate [TETP], an inverse order dependence on [H +], has been observed. The rate is independent of [Mn(II)]. However, an inverse order dependence on varying the dielectric constant using various percentages (v/v) of acetic acid has also been observed, and but addition of anions such as Cl- and ClO4- has insignificant effect on the rate. Activation parameters have been evaluated using the Arrhenius and Erying plots. The oxidation products were isolated and characterized. Based on the results obtained, a plausible mechanism involving [Mn(OAc)4]- has been proposed. An apparent correlation was noted between the rate of oxidation of these TETPs by Mn(III) in the presence of sulfate ions in sulfuric acid medium and Mn(OAc)3 in the acetic acid medium. The rate of oxidation with Mn(OAc)3 was observed to be slower than with the former. The rate of oxidation of GGFP was found to be higher than GGIP, GGVP, and GGAP, This may be due to the presence of an aromatic side chain and/or because of the increased hydrophobicity. The overall order of rate of oxidation of TETPs is GGFP > GGIP > GGVP > GGAP, which also represents an increasing order of their hydrophobicity.
Synthesis and kinetics of oxidation of some dipeptides with anodically generated manganese(III) sulphate: Mechanistic study
Kumara,Channe Gowda,Rangappa
, p. 438 - 444 (2007/10/03)
Dipeptides (DP) namely phenylalanyl-proline (Phe-Pro), isoleucyl-proline (Ile-Pro), and leucyl-proline (Leu-Pro) were synthesized by classical solution method and characterized. The kinetics of oxidation of these DP by Mn(III) have been studied in the presence of sulphate ions in acidic medium at 26°C. The reaction was followed spectrophotometrically at λmax = 500 nm. A first-order dependence of rate on both [Mn(III)]0 and [DP]0 was observed. The rate is independent of the concentration of reduction product, Mn(II), and hydrogen ions. The effects of varying dielectric constant of the medium and addition of anions such as sulphate, chloride, and perchlorate were studied. The activation parameters have been evaluated using Arrhenius and Eyring plots. The oxidation products were isolated and characterized. A mechanism involving the reaction of DP with Mn(III) in the rate-limiting step is suggested.
Asymmetric Hydroformylation of 1,2-Disubstituted Olefins Catalysed by Chiral Phosphinephosphite-Rhodium(I) Complexes
Sakai, Nozomu,Nozaki, Kyoko,Takaya, Hidemasa
, p. 395 - 396 (2007/10/02)
Hydroformylations of internal olefins such as (E)- and (Z)-but-2-ene, (E)- and (Z)-1-phenylprop-1-ene, indene, and 1,2-dihydronaphthalene catalysed by (R,S)-binaphos-RhI complex phosphite> or its enantiomer gave the corresponding oxoaldehydes in up to 97percent enantiomeric excess, e.e.