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Addition Step (addition + step)
Selected AbstractsOsmium-Catalyzed Olefin Dihydroxylation and Aminohydroxylation in the Second Catalytic CycleADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2006Peng Wu Abstract Two catalytic cycles operate in the osmium-catalyzed olefin dihydroxylation and aminohydroxylation. Slow hydrolysis of the Os(VI) monoglycolate (or monoazaglycolate in aminohydroxylation) intermediate often results in the addition of another molecule of olefin thereby shunting the catalysis into the second catalytic cycle. As a result, both enantio- and chemoselectivity are reduced. A series of new chelating ligands were devised, which force the catalysis into the second cycle while maintaining enantiocontrol in the olefin addition step. Excellent catalytic turnover and moderate to good enantioselectivity were achieved. [source] A theoretical study on the catalytic mechanism of Mus musculus adenosine deaminaseJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2010Xian-Hui Wu Abstract The catalytic mechanism of Mus musculus adenosine deaminase (ADA) has been studied by quantum mechanics and two-layered ONIOM calculations. Our calculations show that the previously proposed mechanism, involving His238 as the general base to activate the Zn-bound water, has a high activation barrier of about 28 kcal/mol at the proposed rate-determining nucleophilic addition step, and the corresponding calculated kinetic isotope effects are significantly different from the recent experimental observations. We propose a revised mechanism based on calculations, in which Glu217 serves as the general base to abstract the proton of the Zn-bound water, and the protonated Glu217 then activates the substrate for the subsequent nucleophilic addition. The rate-determining step is the proton transfer from Zn-OH to 6-NH2 of the tetrahedral intermediate, in which His238 serves as a proton shuttle for the proton transfer. The calculated kinetic isotope effects agree well with the experimental data, and calculated activation energy is also consistent with the experimental reaction rate. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Correcting illegitimate rank reversals: proper adjustment of criteria weights prevent alleged AHP intransitivityJOURNAL OF MULTI CRITERIA DECISION ANALYSIS, Issue 5-6 2008Diederik J. D. Wijnmalen Abstract This note comments on a paper by Triantaphyllou (J. Multi-Crit. Decis. Anal. 2001; 10: 11,25) that attempts to demonstrate new types of rank reversal that can occur with the analytic hierarchy process (AHP). He contends that the reversals are attributable to the various types of normalization that are used with the addition step in AHP synthesis. His paper goes on to suggest that the multiplicative AHP should be used instead. This note shows that the cause of the problem is another one: AHP's independence axiom, which prohibits adjusting the criteria weights when the set of alternatives or the type of normalization change. If the criteria weights are adjusted properly, none of the rank reversals will occur. Copyright © 2009 John Wiley & Sons, Ltd. [source] Kinetics and Molecular Weight Development of Dithiolactone-Mediated Radical Polymerization of StyreneMACROMOLECULAR REACTION ENGINEERING, Issue 4 2009Jesús Guillermo Soriano-Moro Abstract Calculations of polymerization kinetics and molecular weight development in the dithiolactone-mediated polymerization of styrene at 60,°C, using 2,2,-azobisisobutyronitrile (AIBN) as initiator and , -phenyl- , -butirodithiolactone (DTL1) as controller, are presented. The calculations were based on a polymerization mechanism based on the persistent radical effect, considering reverse addition only, implemented in the PREDICI® commercial software. Kinetic rate constants for the reverse addition step were estimated. The equilibrium constant (K,=,kadd/k -add) fell into the range of 105,106 L,·,mol,1. Fairly good agreement between model calculations and experimental data was obtained. [source] Mechanistic Investigation of Chiral Phosphoric Acid Catalyzed Asymmetric Baeyer,Villiger Reaction of 3-Substituted Cyclobutanones with H2O2 as the OxidantCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2010Senmiao Xu Dr. Abstract The mechanism of the chiral phosphoric acid catalyzed Baeyer,Villiger (B,V) reaction of cyclobutanones with hydrogen peroxide was investigated by using a combination of experimental and theoretical methods. Of the two pathways that have been proposed for the present reaction, the pathway involving a peroxyphosphate intermediate is not viable. The reaction progress kinetic analysis indicates that the reaction is partially inhibited by the ,-lactone product. Initial rate measurements suggest that the reaction follows Michaelis,Menten-type kinetics consistent with a bifunctional mechanism in which the catalyst is actively involved in both carbonyl addition and the subsequent rearrangement steps through hydrogen-bonding interactions with the reactants or the intermediate. High-level quantum chemical calculations strongly support a two-step concerted mechanism in which the phosphoric acid activates the reactants or the intermediate in a synergistic manner through partial proton transfer. The catalyst simultaneously acts as a general acid, by increasing the electrophilicity of the carbonyl carbon, increases the nucleophilicity of hydrogen peroxide as a Lewis base in the addition step, and facilitates the dissociation of the OH group from the Criegee intermediate in the rearrangement step. The overall reaction is highly exothermic, and the rearrangement of the Criegee intermediate is the rate-determining step. The observed reactivity of this catalytic B,V reaction also results, in part, from the ring strain in cyclobutanones. The sense of chiral induction is rationalized by the analysis of the relative energies of the competing diastereomeric transition states, in which the steric repulsion between the 3-substituent of the cyclobutanone and the 3- and 3,-substituents of the catalyst, as well as the entropy and solvent effects, are found to be critically important. [source] Computational Investigations on the General Reaction Profile and Diastereoselectivity in Sulfur Ylide Promoted AziridinationCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2007Deepa Janardanan Abstract Mechanism and diastereoselectivity of sulfur ylide promoted aziridination reactions were studied by density functional theory with inclusion of solvent effects through the continuum solvation model. The general reaction pathway was modeled for the addition of substituted sulfur ylides (Me2S+CH,R) to an aldimine ((E)-methyl ethylidenecarbamate, MeHCNCO2Me). The nature of the substituents on the ylidic carbon atom substantially affects the reaction profile. The stabilized (R=COMe) and semistabilized (R=Ph) ylides follow a cisoid addition mode leading to trans aziridines via anti betaine intermediates. The simplest model ylide (unstabilized, R=H) underwent cisoid addition in a similar fashion. In the case of stabilized ylides product diastereoselectivity is controlled by the barriers of the elimination step leading to the 2,3- trans aziridine, whereas it is decided in the addition step in the case of semistabilized ylides. The importance of steric and electronic factors in diastereoselective addition (2 and 5) and elimination (5) transition states was established. Comparison of results obtained with the gas-phase optimized geometries and with the fully optimized solvent-phase geometries reveals that the inclusion of solvent effects does not bring about any dramatic changes in the reaction profiles for all three kinds of ylides. In particular, diastereoselectivity for both kinds of ylides was found to be nearly the same in both these approaches. [source] Generalization of multivariate optical computations as a method for improving the speed and precision of spectroscopic analysesJOURNAL OF CHEMOMETRICS, Issue 6 2008Marc K. Boysworth Abstract Multivariate optical computations (MOCs) offer improved analytical precision and increased speed of analysis via synchronous data collection and numerical computation with scanning spectroscopic systems. The improved precision originates in the redistribution of integration time from spurious channels to informative channels in an optimal manner for increasing the signal-to-noise ratio with multivariate analysis under the constraint of constant total analysis time. In this work, MOCs perform the multiplication and addition steps of spectral processing by adjusting the integration parameters of the optical detector or adjusting the scanning profile of the tunable optical filter. Improvement in the precision of analysis is achieved via the implicit optimization of the analytically useful signal-to-noise ratio. The speed improvements are realized through simpler data post-processing, which reduces the computation time required after data collection. Alternatively, the analysis time may be significantly truncated while still seeing an improvement in the precision of analysis, relative to competing methods. Surface plasmon resonance (SPR) spectroscopic sensors and visible reflectance spectroscopic imaging were used as test beds for assessing the performance of MOCs. MOCs were shown to reduce the standard deviation of prediction by 15% compared to digital data collection and analysis with the SPR and up to 45% for the imaging applications. Similarly, a 30% decrease in the total analysis time was realized while still seeing precision improvements. Copyright © 2008 John Wiley & Sons, Ltd. [source] | ||||||||||