Mechanistic identity

In this reaction, an equilibrium is set up. The nucleophile, iodide, is the same as the leaving group. Therefore, inversion of configuration merely converts the (-l-)-isomer into the (—)-isomer. As a result, the optical activity gradually disappears and ultimately becomes zero as the mixture becomes the racemic ( )-form. We are never going to get complete conversion of the (-1-)- into (—)-enantiomer because the reverse reaction will also occur. This is mechanistically identical to the forward reaction, so either (-1-)- or (—)-2-iodobutane as starting material would give racemic product, i.e. it is a racemization reaction. 

Stevens and Strickler (1973) obtained an a value of about 1 for the dedeuteration of naphthalene in sulphuric acid while Johnson, Katritzky and O Neill (1974) observed values of 0-83 at the 1 position and 0-64 at the 2 position for the mechanistically identical detritiation reaction. 

Horseradish peroxidase is an excellent candidate with which to elucidate enzymatic kinetics in organic solvents. It is an active enzyme with turnover numbers exceeding 320 s 1 in organic media (XI) and hence is susceptible to diffusional limitations which must be overcome. Peroxidase also catalyzes mechanistically identical reactions in aqueous and organic media. Therefore, direct kinetic comparisons between aqueous and organic reactions can be made and the effects of the organic solvent on reactivity and substrate specificity can be directly compared to aqueous-based catalysis. 

Strengths of the substrate C-H bond which is broken and that of the O-H bond which is being formed. The successful application of Evans-Polanyi correlations of the type shown in Fig. 17.6 for transition metal oxidants has led to the generalization that these reactions proceed by a synchronous PCET process that is mechanistically identical to hydrogen abstraction by an organic radical oxidant [52, 54]. 

DNA DNA hybrids. If heat-denatured DNA (see Melting point of DNA) is allowed to cool slowly, double-stranded molecules may be reformed, i.e. the single strands reassociate or become annealed. When two different DNAs are denatured in the presence of each other, the annealed mixture will include hybrid molecules, providing the two DNAs have some base sequences in common. Reassociation and H. (both can be called annealing) are therefore kinetically and mechanistically identical. The following conditions are required for efficient reassociation or hybridization of denatured DNA ... 

Fig. 2. Nucleic acid sequencing. Postulated mechanism of the reactions involved in the cleavage of DNA by removal of a 2-deoxythymidine residue. Two fragments are produced, one from the 5 -side, the other from the 3 -side. NB cleavage of the enamine produced by the reaction sequence shown is mechanistically identical to that shown in Fig.1.

Proton transfer reactions such as the ones above are mechanistically identical to Sn2 reactions. By analogy with Sn2, identify the nucleophile, electrophilic atom, and leaving group for each. 

When the addition and elimination reactions are mechanically reversible, they proceed by identical mechanistic paths but in opposite directions. In these circumstances, mechanistic conclusions about the addition reaction are applicable to the elimination reaction and vice versa. The principle of microscopic reversibility states that the mechanism (pathway) traversed in a reversible reaction is the same in the reverse as in the forward direction. Thus, if an addition-elimination system proceeds by a reversible mechanism, the intermediates and transition states involved in the addition process are the same as... 

The general mechanistic framework outlined in this section must be elaborated by other details to fully describe the mechanisms of the individual electrophilic substitutions. The question of the identity of the active electrophile in each reaction is important. We have discussed the case of nitration, in which, under many circumstances, the electrophile is the nitronium ion. Similar questions arise in most of the other substitution reactions. 

Curvature in a Br nsted-type plot is sometimes attributed to a change in transition state structure. This is not a change in mechanism rather it is interpreted as a shift in extent of bond cleavage and bond formation within the same mechanistic pattern. Thus, Ba-Saif et al. ° found curvature in the Br nsted-type plot for the identity reactions in acetyl transfer between substituted phenolates this reaction was shown earlier. They concluded that a change in transition state structure occurs in the series. Jencks et al." caution against this type of conclusion solely on the evidence of curvature, because of the other possible causes. 

Nothing is known about the identity of the iron species responsible for dehydrogenation of the substrate. Iron-oxo species such as FeIV=0 or Fem-OOH are postulated as the oxidants in most heme or non-heme iron oxygenases. It has to be considered that any mechanistic model proposed must account not only for the observed stereochemistry but also for the lack of hydroxylation activity and its inability to convert the olefinic substrate. Furthermore, no HppE sequence homo-logue is to be found in protein databases. Further studies should shed more light on the mechanism with which this unique enzyme operates. 

If we look at the mechanistic and crystallographic aspects of the operation of polycomponent electrodes, we see that the incorporation of electroactive species such as lithium into a crystalline electrode can occur in two basic ways. In the examples discussed above, and in which complete equilibrium is assumed, the introduction of the guest species can either involve a simple change in the composition of an existing phase by solid solution, or it can result in the formation of new phases with different crystal structures from that of the initial host material. When the identity and/or amounts of phases present in the electrode change, the process is described as a reconstitution reaction. That is, the microstructure is reconstituted. 

Another type of NR crosstalk, which has only recently been recognized, is the so-called nongenomic actions of several receptors that induce very rapid cellular effects. Effectively, evidence has accumulated over several decades that steroid receptors may have a role that does not require their transcriptional activation, such as modifying the activity of enzymes and ion channels. While the effects of steroids that are mediated by the modulation of gene expression do occur with a time lag of hours, steroids can induce an increase in several second messengers such as inositol triphosphate, cAMP, Ca2+, and the activation of MARK and PI3 kinase within seconds or minutes. Many mechanistic details of these nongenomic phenomena remain poorly understood. Notably, controversy still exists as to the identity of the receptors that initiate the non-genomic steroid actions. However, it now appears that at least some of the reported effects can be attributed to the same steroid receptors that are known as NRs. 

The identity in sign and similarity in optical rotations of sultones (+)-52A,B, obtained from (—)-49A and (+)-49B, indicate that the absolute configuration of the y-carbon in both sultones as well as in both sultines is the same. In conclusion, the authors suggested113,114 that of the four possibilities shown below, y-sultines 48A-51A and 48B-51B may be assigned the (R)c-(Sf and (R)c-(Rf absolute configurations, respectively. Although initiated by mechanistic interest, this study has also resulted in a new method for selective synthesis of... 

Kinetic studies using 1,9-decadiene and 1,5-hexadiene in comparison widi catalyst 14 and catalyst 12 demonstrate an order-of-magnitude difference in their rates of polymerization, widi 14 being the faster of the two.12 Furdier, this study shows diat different products are produced when die two catalysts are reacted widi 1,5-hexadiene. Catalyst 14 generates principally lineal" polymer with the small amount of cyclics normally observed in step condensation chemistry, while 12 produces only small amounts of linear oligomers widi die major product being cyclics such as 1,5-cyclooctadiene.12 Catalyst 12, a late transition metal benzylidene (carbene), has vastly different steric and electronic factors compared to catalyst 14, an early transition metal alkylidene. Since die results were observed after extended reaction time periods and no catalyst quenching or kinetic product isolation was performed, this anomaly is attributed to mechanistic differences between diese two catalysts under identical reaction conditions. 

Chapter 11 analyzes the recently discovered mechanistic equivalence of electrochemical promotion and metal-support interactions on ionic and mixed conducting supports containing Zr02, Ce02 or Ti02. The analysis focuses on the functional identity and operational differences of promotion, electrochemical promotion and metal support interactions. 

Ideally, it would be desirable to determine many parameters in order to characterize and mechanistically define these unusual reactions. This has been an important objective that has often been considered in the course of these studies. It would be helpful to know, as a function of such parameters of the plasma as the radio-frequency power, pressure, and rate of admission of reactants, (2) the identity and concentrations of all species, including trifluoromethyl radicals, (2) the electronic states of each species, (3) the vibrational states of each species, and (4) both the rotational states of each species and the average, translational energies of, at least, the trifluoromethyl radicals. 

A number of mechanistically distinct enzymes can likewise be employed for the synthesis of product structures identical to those accessible from aldolase catalysis. Such alternative cofactor-dependent enzymes (e.g. transketolase) are emerging as useful catalysts in organic synthesis. As these operations often extend and/or... 

The simple porphyrin category includes macrocycles that are accessible synthetically in one or few steps and are often available commercially. In such metallopor-phyrins, one or both axial coordinahon sites of the metal are occupied by ligands whose identity is often unknown and cannot be controlled, which complicates mechanistic interpretation of the electrocatalytic results. Metal complexes of simple porphyrins and porphyrinoids (phthalocyanines, corroles, etc.) have been studied extensively as electrocatalysts for the ORR since the inihal report by Jasinsky on catalysis of O2 reduction in 25% KOH by Co phthalocyanine [Jasinsky, 1964]. Complexes of all hrst-row transition metals and many from the second and third rows have been examined for ORR catalysis. Of aU simple metalloporphyrins, Ir(OEP) (OEP = octaethylporphyrin Fig. 18.9) appears to be the best catalyst, but it has been little studied and its catalytic behavior appears to be quite distinct from that other metaUoporphyrins [CoUman et al., 1994]. Among the first-row transition metals, Fe and Co porphyrins appear to be most active, followed by Mn [Deronzier and Moutet, 2003] and Cr. Because of the importance of hemes in aerobic metabolism, the mechanism of ORR catalysis by Fe porphyrins is probably understood best among all metalloporphyrin catalysts. 

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