General. All reactions were performed under argon using Schlenk techniques. Diethyl ether and THF were freshly distilled from sodium/benzophenone prior to use. 1 H, 13 C and 31 P spectra were recorded on a 400 MHz and 300 MHz spectrometers. Chemical shifts (ppm) were reported and referenced to the internal signal of residual protic solvent. High resolution mass spectral analyses (HRMS) were per...

Initially, the Atherton-Todd (AT) reaction was applied for the synthesis of phosphoramidates by reacting dialkyl phosphite with a primary amine in the presence of carbon tetrachloride. These reaction conditions were subsequently modified with the aim to optimize them and the reaction was extended to different nucleophiles. The mechanism of this reaction led to controversial reports over the pas...

We have observed that high SOD-like function (decomposition of superoxide anion) was observed for several iron(III) compounds with tripodal ligands and several oxovanadium(IV) compounds, and also that these compounds exhibit high catalytic activity for oxidative cleavage of 3,5-di-tert-butylcatechol in non-donating solvents such as dichloromethane or nitromethane. These are suggesting that the ...

The interconversion of dihydroxyacetone phosphate and glyceraldehyde 3-phosphate catalyzed by the enzyme triosephosphate isomerase was first demonstrated by Meyerhof and Kiessling (1). Since then studies with the enzyme have disclosed little about the mechanism of this reaction. Such an interconversion may be envisioned as occurring by formation of an enediol as, based on chemical analogy (2)) ...

1. A stable ternary complex of salicylate hydroxylase apoenzyme, flavin adenine dinucleotide, and salicylate was detected by a change of the absorption spectrum and by titration of the holoenzyme with salicylate. 2. The complex was enzymatically active, since the stoichiometric formation of the product, catechol, was observed upon introduction of air into a solution of reduced form of the compl...

The copper-mediated aromatic nucleophilic substitution reactions developed by Fritz Ullmann and Irma Goldberg required stoichiometric amounts of copper and very high reaction temperatures. Recently, it was found that addition of relatively cheap ligands (diamines, aminoalcohols, diketones, diols) made these reactions truly catalytic, with catalyst amounts as low as 1 mol% or even lower. Since t...

Based on their observations that the lipoxidase-catalyzed oxidation of linoleate, like autoxidation, gave primarily conjugated diene peroxides (1,2) and caused a coupled oxidation of some easily oxidizable substances, such as carotenoids (3) and antioxidants (4), Bergstrom and Holman proposed a reaction mechanism for lipoxidase catalysis. They suggested (4) that lipoxidase could cause initiatio...

The activation mechanisms of recombinant N-methyl-d-aspartate receptors (NRs) have been established in sufficient detail to account for their single channel and macroscopic responses; however, the reaction mechanism of native NRs remains uncertain due to indetermination of the isoforms expressed and possible neuron-specific factors. To delineate the activation mechanism of native NRs, we examin...

A study of the exchange reactions between adenosine triphosphate and either radioactive inorganic phosphate, or adenosine diphosphate (l), catalyzed by propionyl carboxylase, showed that inorganic phosphate was required for adenosine triphosphate-adenosine diphosphate exchange and, conversely, adenosine diphosphate was required for adenosine triphosphateinorganic phosphate exchange. A requireme...

We introduce KiNetX, a fully automated meta-algorithm for the kinetic simulation and analysis of general (complex and noisy) chemical reaction networks with rigorous uncertainty control. It is designed to cope with method inherent errors in quantum chemical calculations on elementary reaction steps. We developed and implemented KiNetX to possess three features. First, KiNetX identifies and elim...