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Concerted Mechanism (concerted + mechanism)
Selected AbstractsAnalysis of Linear Free-Energy Relationships Combined with Activation Parameters Assigns a Concerted Mechanism to Alkaline Hydrolysis of X-Substituted Phenyl DiphenylphosphinatesCHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2008Ik-Hwan Um Prof. Abstract A kinetic study is reported for alkaline hydrolysis of X-substituted phenyl diphenylphosphinates (1,a,i). The Brønsted-type plot for the reactions of 1,a,i is linear over 4.5 pKa units with ,lg=,0.49, a typical ,lg value for reactions which proceed through a concerted mechanism. The Hammett plots correlated with ,o and ,, constants are linear but exhibit many scattered points, while the corresponding Yukawa,Tsuno plot results in excellent linear correlation with ,=1.42 and r=0.35. The r value of 0.35 implies that leaving-group departure is partially advanced at the rate-determining step (RDS). A stepwise mechanism, in which departure of the leaving group from an addition intermediate occurs in the RDS, is excluded since the incoming HO, ion is much more basic and a poorer nucleofuge than the leaving aryloxide. A dissociative (DN + AN) mechanism is also ruled out on the basis of the small ,lg value. As the substituent X in the leaving group changes from H to 4-NO2 and 3,4-(NO2)2, ,H,, decreases from 11.3,kcal,mol,1 to 9.7 and 8.7,kcal,mol,1, respectively, while ,S,, varies from ,22.6,cal,mol,1,K,1 to ,21.4 and ,20.2,cal,mol,1,K,1, respectively. Analysis of LFERs combined with the activation parameters assigns a concerted mechanism to the current alkaline hydrolysis of 1,a,i. [source] Theoretical Study on Hetero-Diels,Alder Reaction of Butadiene with Benzaldehyde Catalyzed by Chiral InIII ComplexesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2010Xiuli Cao Abstract The mechanism of the hetero-Diels,Alder reaction of butadiene with benzaldehyde catalyzed by chiral N,N, -dioxide/In(OTf)3 complexes was studied theoretically by using density functional theory (DFT) and model system. The computational results indicate that the catalyzed reaction proceeded through a concerted mechanism via a highly zwitterionic transition state. The lowest energy barrier was 11.8 kJ,mol,1, which is 63.0 kJ,mol,1 lower than that of the uncatalyzed reaction. The results indicate that the endo approach is advantageous over the exo approach, because exo transitions states suffer from more steric hindrance than the endo transitions states as a result of interactions among the substrates, the trifluoromethanesulfonic group and the R4 groups of the ligand. The (S) configuration was observed predominantly over the (R) form, because there is no distinguishable repulsion between butadiene and the exo amino side or the endo amino side of the ligand. Besides, the interactions between the terminal hydrogen atoms of butadiene and the oxygen atoms of the trifluoromethanesulfonic group make the structure more stable. Thus, the experimental results were explained well by calculation of the chiral N,N, -dioxide/In(OTf)3 complex catalyzed hetero-Diels,Alder reaction at the molecular level. [source] Hydrogen Evolution from Peroxides , a Concerted ReactionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2004Werner R. Thiel Abstract DFT calculations provide strong evidence that the evolution of hydrogen from mixtures of aldehydes and hydrogen peroxide proceeds by a concerted mechanism. The electronic influence of a series of substituents is correlated with the enthalpies of activation and reaction, and the calculated isotope effect of the reaction is compared with experimentally obtained data. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Side chain specificity of ADP-ribosylation by a sirtuinFEBS JOURNAL, Issue 23 2009Kamau Fahie Endogenous mono-ADP-ribosylation in eukaryotes is involved in regulating protein synthesis, signal transduction, cytoskeletal integrity, and cell proliferation, although few cellular ADP-ribosyltransferases have been identified. The sirtuins constitute a highly conserved family of protein deacetylases, and several family members have also been reported to perform protein ADP-ribosylation. We characterized the ADP-ribosylation reaction of the nuclear sirtuin homolog Trypanosoma brucei SIR2-related protein 1 (TbSIR2RP1) on both acetylated and unacetylated substrates. We demonstrated that an acetylated substrate is not required for ADP-ribosylation to occur, indicating that the reaction performed by TbSIR2RP1 is a genuine enzymatic reaction and not a side reaction of deacetylation. Biochemical and MS data showed that arginine is the major ADP-ribose acceptor for unacetylated substrates, whereas arginine does not appear to be the major ADP-ribose acceptor in reactions with acetylated histone H1.1. We performed combined ab initio quantum mechanical/molecular mechanical molecular dynamics simulations, which indicated that sirtuin ADP-ribosylation at arginine is energetically feasible, and involves a concerted mechanism with a highly dissociative transition state. In comparison with the corresponding nicotinamide cleavage in the deacetylation reaction, the simulations suggest that sirtuin ADP-ribosylation would be several orders slower but less sensitive to nicotinamide inhibition, which is consistent with experimental results. These results suggest that TbSIR2RP1 can perform ADP-ribosylation using two distinct mechanisms, depending on whether or not the substrate is acetylated. Structured digital abstract ,,MINT-7288298: TbSIR2 (uniprotkb:O96670) adp ribosylates (MI:0557) histone H1.1 (uniprotkb:Q02539) by enzymatic studies (MI:0415) ,,MINT-7288305, MINT-7288325, MINT-7288338, MINT-7288352, MINT-7288370, MINT-7288395, MINT-7288412: TbSIR2 (uniprotkb:O96670) adp ribosylates (MI:0557) histone H1.1 (uniprotkb:P02253) by enzymatic studies (MI:0415) ,,MINT-7288385: TbSIR2 (uniprotkb:O96670) deacetylates (MI:0197) histone H1.1 (uniprotkb:Q02539) by deacetylase assay (MI:0406) ,,MINT-7288424: hADPRH (uniprotkb:P54922) cleaves (MI:0194) histone H1.1 (uniprotkb:Q02539) by enzymatic studies (MI:0415) [source] Kinetics and mechanism of the aminolysis of dimethyl and methyl phenyl phosphinic chlorides with anilinesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2009Nilay Kumar Dey Abstract The reactions of dimethyl phosphinic chloride (1) and methyl phenyl phosphinic chloride (2) with X-anilines have been studied kinetically in acetonitrile at 15.0 and 55.0,°C, respectively. The deuterium kinetic isotope effects (KIEs) involving deuterated aniline nucleophiles (XC6H4ND2) are also reported for the same reactions. The obtained KIEs for 1 are secondary inverse (kH/kD,=,0.703,0.899,<,1), while those for 2 are primary normal (kH/kD,=,1.62,2.10,>,1). A concerted mechanism involving predominantly backside nucleophilic attack is proposed for the anilinolysis of 1. A concerted mechanism involving predominantly frontside attack via a hydrogen-bonded four-center-type transition state is proposed for the anilinolysis of 2. The degree of steric hindrance is the major factor that determines both the reactivity of the phosphinates and the direction of the nucleophilic attack on the phosphinates. Copyright © 2008 John Wiley & Sons, Ltd. [source] Effect of substitution of oxygen by sulfur in the nonleaving group of a carbonate: kinetics of the phenolysis and benzenethiolysis of S -methyl aryl thiocarbonatesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8 2007Enrique A. Castro Abstract The phenolysis and benzenethiolysis of S -methyl 4-nitrophenyl thiocarbonate (1) and S -methyl 2,4-dinitrophenyl thiocarbonate (2) in water are studied kinetically. The Brønsted plots (log kNversus nucleophile basicity) are linear for all reactions. The Brønsted slopes for 1 and 2 are, 0.51 and 0.66 (phenolysis) and 0.55 and 0.70 (benzenethiolysis), respectively. These values suggest a concerted mechanism for these reactions, as found in the corresponding carbonates. Namely, substitution of OMe by SMe in the nonleaving group does not change the mechanism. Copyright © 2007 John Wiley & Sons, Ltd. [source] Mechanistic studies of intramolecular CH insertion reaction of arylnitrenes: isotope effect, configurational purity and radical clock studiesJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 1 2005Shigeru Murata Abstract In order to reveal the mechanism of the intramolecular CH insertion of arylnitrenes, three experiments were carried out: measurement of isotope effects, determination of the extent of configurational retention and radical clock studies. Irradiation of the deuterium-substituted azide 4 - d in an inert solvent exclusively afforded the indolines 5 - h and 5 - d, in which the kinetic isotope effect kH/kD on the intramolecular CH insertion of the nitrene was evaluated as 12.6,14.7 at room temperature. A chiral chromatographic analysis of the indoline 11 obtained from the optically active azide (S)- 6 revealed that the enantiomeric purity of the starting azide was almost completely lost during the intramolecular CH insertion of the photolytically generated nitrene (enantiomeric excess <10%). The thermolysis of the azide 7 at 180°C mainly gave a mixture of the cyclopropyl ring-opened products 20,22, together with the intramolecular CH insertion product with an intact cyclopropyl ring 19. On the basis of these observations, we concluded that the intramolecular CH insertion of the nitrene proceeds primarily by the hydrogen abstraction,recombination mechanism. We propose, however, a small contribution of the concerted mechanism to the intramolecular CH insertion, based on the solvent dependence of the isotope effect and the extent of the configurational retention. Copyright © 2004 John Wiley & Sons, Ltd. [source] Electrospray ionization mass spectrometric study of end-groups in peroxydicarbonate-initiated radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2008Michael Buback Abstract Initiation by diethyl peroxydicarbonate (E-PDC), di- n -tetradecyl peroxydicarbonate (nTD-PDC), di- n -hexadecyl peroxydicarbonate (nHD-PDC), and di-2-ethylhexyl peroxydicarbonate (2EH-PDC) of free-radical polymerizations of methyl methacrylate in benzene solution was studied by end-group analysis via electrospray ionization mass spectrometry (ESI-MS). Unambiguous assignment of ESI-MS peaks allows for identification of the type of radical that starts chain growth. In case of initiation by dialkyl peroxydicarbonates with linear alkyl groups, almost exclusively alkoxy carbonyloxyl species, which are the primary fragments from initiator decomposition, occur as end-groups. With 2EH-PDC, however, both the primary 2-ethylhexoxy carbonyloxyl fragment and a second moiety, which is formed by decarboxylation of the 2-ethylhexoxy carbonyloxyl radical, are clearly observed as end-groups. The decarboxylation process is described by a concerted mechanism which involves a 1,5-hydrogen shift reaction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6071,6081, 2008 [source] Mass spectrometric characterization of 4-oxopentanoic acid and gas-phase ion fragmentation mechanisms studied using a triple quadrupole and time-of-flight analyzer hybrid system and density functional theoryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2008Basem Kanawati 4-Oxopentanoic acid was characterized experimentally by electrospray ionization using a triple quadrupole and time-of-flight analyzer hybrid system. This compound was chosen as a model substance for small organic compounds bearing an acetyl and a carboxyl group. Collision-induced dissociation experiments at different activation energies were performed to elucidate possible fragmentation pathways. These pathways were also studied on the theoretical level using density functional theory (DFT) B3LYP/6-311++G(3df,3pd)//B3LYP/6-31+G(d)+ZPVE calculations. CO2 ejection from the [M,H], anion of 4-oxopentanoic acid was observed and the fragmentation pathway studied by DFT reveals a new concerted mechanism for CO2 elimination accompanied by an intramolecular proton transfer within a pentagonal transition state structure. Successive elimination of water and CO from the [M,H], anion of 4-oxopentanoic acid was also observed. A rearrangement in the primary deprotonated ketene anion produced after water elimination was found on the theoretical level and leads to CO elimination from the primary product anion [M,H,H2O],. Energy diagrams along the reaction coordinates of the fragmentation pathways are presented and discussed in detail. Mulliken charge distributions of some important structures are presented. Copyright © 2008 John Wiley & Sons, Ltd. [source] Analysis of Linear Free-Energy Relationships Combined with Activation Parameters Assigns a Concerted Mechanism to Alkaline Hydrolysis of X-Substituted Phenyl DiphenylphosphinatesCHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2008Ik-Hwan Um Prof. Abstract A kinetic study is reported for alkaline hydrolysis of X-substituted phenyl diphenylphosphinates (1,a,i). The Brønsted-type plot for the reactions of 1,a,i is linear over 4.5 pKa units with ,lg=,0.49, a typical ,lg value for reactions which proceed through a concerted mechanism. The Hammett plots correlated with ,o and ,, constants are linear but exhibit many scattered points, while the corresponding Yukawa,Tsuno plot results in excellent linear correlation with ,=1.42 and r=0.35. The r value of 0.35 implies that leaving-group departure is partially advanced at the rate-determining step (RDS). A stepwise mechanism, in which departure of the leaving group from an addition intermediate occurs in the RDS, is excluded since the incoming HO, ion is much more basic and a poorer nucleofuge than the leaving aryloxide. A dissociative (DN + AN) mechanism is also ruled out on the basis of the small ,lg value. As the substituent X in the leaving group changes from H to 4-NO2 and 3,4-(NO2)2, ,H,, decreases from 11.3,kcal,mol,1 to 9.7 and 8.7,kcal,mol,1, respectively, while ,S,, varies from ,22.6,cal,mol,1,K,1 to ,21.4 and ,20.2,cal,mol,1,K,1, respectively. Analysis of LFERs combined with the activation parameters assigns a concerted mechanism to the current alkaline hydrolysis of 1,a,i. [source] | ||||||||||