1730-97-8Relevant academic research and scientific papers
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.
Solvent-free asymmetric olefin hydroformylation catalyzed by highly cross-linked polystyrene-supported (R,S)-BINAPHOS-Rh(I) complex
Shibahara, Fumitoshi,Nozaki, Kyoko,Hiyama, Tamejiro
, p. 8555 - 8560 (2007/10/03)
Using an (R,S)-BINAPHOS-Rh(I) catalyst that is covalently anchored to a highly cross-linked polystyrene support, asymmetric hydroformylation of olefins was performed in the absence of organic solvents. The reaction of cis-2-butene, a gaseous substrate, provided (S)-2-methylbutanal with 100% regioselectivity and 82% ee upon treatment with H2 (12 atm) and CO (12 atm) in a batchwise reactor equipped with a fixed bed. The polymer-supported catalyst was applicable to a continuous vapor-flow column reactor, and thus, 3,3,3-trifluoropropene was converted into (S)-2-trifluoromethylpropanal with an iso/normal ratio of 95/5 and 90% ee. Less volatile olefins, such as styrene, vinyl acetate, 1-alkenes, and fluorinated alkenes, were successfully converted into the corresponding isoaldehydes with high ee values, when they were injected through a supercritical CO2-flow column reactor. Successive injection of a series of olefins realized the conversion of an olefin library into an optically active aldehyde library.
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.
Synthesis of New Chiral Phosphinephosphites Having 2-Diphenylphosphinobiphenyl-2'-yl Backbone and Their Use in Rh(I)-Catalyzed Asymmetric Hydroformylations
Higashizima, Takanori,Sakai, Nozomu,Nozaki, Kyoko,Takaya, Hidemasa
, p. 2023 - 2026 (2007/10/02)
New chiral phosphinephosphites (R)-(5,5'-dichloro-2-diphenylphosphino-4,4',6,6'-tetramethylbiphenyl-2'-yl)(S)-1,1'-binaphthalen-2,2'-diyl)phosphite and its enantiomer (S,R)-BIPHEMPHOS have been synthesized from 5,5'-dichloro-4,4',6,6'-tetramethyl-2,2'-biphenyldiol in enantiomerically pure form.Their Rh(I) complexes have been shown to be highly efficient catalysts for asymmetric hydroformylations of a variety of olefinic substrates.The corresponding phosphinephosphites derived from 2,2'-biphenyldiol were also tested as ligands for asymmetric hydroformylation.
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.
TOTAL SYNTHESIS OF (-)-BETAENONE C
Ichihara, Akitami,Miki, Shokyo,Kawagishi, Hirokazu,Sakamura, Sadao
, p. 4551 - 4554 (2007/10/02)
Stereoselctive synthesis of (-)-betaenone C through intramolecular Diels-Alder reaction has made possible to provide pertinent intermediates for the biosynthetic study of betaenones.
Stereoselective Synthesis of Alcohols, XI. Double Stereodifferentiation in the Addition of Crotylboronates to Aldehydes: Prelog-Djerassi Lactone
Hoffmann, Reinhard W.,Zeiss, Hans-Joachim,Ladner, Wolfgang,Tabche, Susanne
, p. 2357 - 2370 (2007/10/02)
Addition of the (Z)-crotylboronate 11 to (S)-(+)-α-methylbutyraldehyde (4) resulted in the Cram and Anti-Cram diastereomers 6 and 7.Their ratio depended on the chirality of the boronate component.Hence the formation of the alcohol 7 could be favoured by double stereodifferentiation.Similarly, on addition of the (E)-crotylboronate 12 predominant formation of the isomer 13 could be achieved.These observations formed the basis for a stereoselective synthesis of the Prelog-Djerassi lactone 3.
