Polar concerted reaction mechanisms

Turning to pathway c), the concerted-reaction mechanism, we have formulated two approaches to predicting the rate constant, a double-adiabatic and a two-dimensional approach (4,5). In the double-adiabatic theory, the electron is considered to be coupled to two nuclear modes, a solvent (orientational polarization) mode that is treated classically in view of its low... 

Some systematic studies on the different reaction schemes and how they are realized in organic reactions were performed some time ago [18]. Reactions used in organic synthesis were analyzed thoroughly in order to identify which reaction schemes occur. The analysis was restricted to reactions that shift electrons in pairs, as either a bonding or a free electron pair. Thus, only polar or heteiolytic and concerted reactions were considered. However, it must be emphasized that the reaction schemes list only the overall change in the distribution of bonds and ftee electron pairs, and make no specific statements on a reaction mechanism. Thus, reactions that proceed mechanistically through homolysis might be included in the overall reaction scheme. 

The initial discussion in this chapter will focus on addition reactions. The discussion is restricted to reactions that involve polar or ionic mechanisms. There are other important classes of addition reactions which are discussed elsewhere these include concerted addition reactions proceeding through nonpolar transition states (Chapter 11), radical additions (Chapter 12), photochemical additions (Chapter 13), and nucleophilic addition to electrophilic alkenes (Part B, Chi iter 1, Section 1.10). 

The first three chapters discuss fundamental bonding theory, stereochemistry, and conformation, respectively. Chapter 4 discusses the means of study and description of reaction mechanisms. Chapter 9 focuses on aromaticity and aromatic stabilization and can be used at an earlier stage of a course if an instructor desires to do so. The other chapters discuss specific mechanistic types, including nucleophilic substitution, polar additions and eliminations, carbon acids and enolates, carbonyl chemistry, aromatic substitution, concerted reactions, free-radical reactions, and photochemistry. 

Mechanistic studies have been designed to determine if the concerted cyclic TS provides a good representation of the reaction. A systematic study of all the E- and Z-decene isomers with maleic anhydride showed that the stereochemistry of the reaction could be accounted for by a concerted cyclic mechanism.19 The reaction is only moderately sensitive to electronic effects or solvent polarity. The p value for reaction of diethyl oxomalonate with a series of 1-arylcyclopentenes is —1.2, which would indicate that there is little charge development in the TS.20 The reaction shows a primary kinetic isotope effect indicative of C—H bond breaking in the rate-determining step.21 There is good agreement between measured isotope effects and those calculated on the basis of TS structure.22 These observations are consistent with a concerted process. 

Intramolecular ionic Diels-Alder reactions were carried out in highly polar media to afford carbocyclic ring systems. The strategy, which obviates the need for high temperatures and pressures, features in situ generation of heteroatom-stabUized allyl cations that undergo subsequent (4 + 2) cycloaddition at ambient temperature. Typically, reactions were complete within 1 hour after addition of substrate. Some cycloadducts were the result of a concerted process, whereas others were formed via a stepwise reaction mechanism (Grieco, 1996). 

Three mechanisms can be proposed for the intimate reaction mechanism for c-e, analogous to the organic 2+2 cycloadditions a pericyclic (concerted) mechanism, a diradical mechanism, and a diion mechanism. In view of the polarization of the metal(+) carbon(-) bond, an ionic intermediate maybe expected. The retention of stereochemistry, if sometimes only temporary, points to a concerted mechanism. 

Concerted + n s] cycloadditions are, in principle, forbidden by orbital symmetry [90]. This restriction is bypassed when these reactions occur via zwitterions or biradicals, or by the symmetry-allowed [A + 2 ] process. Since cycloadditions proceeding through zwitterionic intermediates or dipolar activated complexes should be affected by solvent polarity, the investigation of the solvent effects on rates can be of considerable value when considering potential models for the activated complex and the reaction mechanism [91-93]. The possible solvent effects on one-step and two-step cycloaddition reactions are shown schematically in Fig. 5-6 [92] ... 

It has been suggested that the regioselectivity observed in these cycloadditions is due to a reaction mechanism involving concerted bond forming and breaking in an unsynunetrical, highly polarized transition state.Such a postulate seems reasonable, but at present there is litde supporting evidence for it. 

In the context of classical organochemical additions to olefins, these reactions may occur by concerted, polar, and radical mechanisms. Prior coordination of unsaturated substrates and electron transfer pathways also must be considered for reactions that involve metal complexes. Formal 1,2-insertions can proceed by all the mechanisms... 

These aspects introduce different mechanistic patterns expected for the 1,3-DC reactions, as compared with DA cycloadditions (concerted vs stepwise with some zwitterionic character). This result may again be traced to the electrophilicity difference at the ground states of the reacting pairs.39 These results suggest that the description of the reactivity and the reaction mechanism involved in the 1,3-DC processes can be systematized as in the case of the DA cycloadditions. Such a model should be able to determine the charge transfer pattern and to decide which of the partners is acting as nucleophile/electrophile in a polar process, or even to anticipate a concerted pathway in those cases where the electrophilicity/nucleophilicity difference is small. 

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