Concerted Additions

The reactions of 1-azirines with ketenes and ketenimines represent non-concerted additions and are formally different from the additions to 47r-systems of dienes and 1,3-dipolar compounds (73JOC3466, 71CB2786). 

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). 

How do orbital symmetry requirements relate to [4tc - - 2tc] and other cycloaddition reactions Let us constmct a correlation diagram for the addition of butadiene and ethylene to give cyclohexene. For concerted addition to occur, the diene must adopt an s-cis conformation. Because the electrons that are involved are the n electrons in both the diene and dienophile, it is expected that the reaction must occur via a face-to-face rather than edge-to-edge orientation. When this orientation of the reacting complex and transition state is adopted, it can be seen that a plane of symmetry perpendicular to the planes of the... 

The authors suggested a concerted addition of hydrogen via a six-centered transition state that would produce 12 directly from the olefin (11) (61). Addition of pyridine or quinoline alters the reaction, but it remains complex. 

Although the nucleophilic addition of secondary amines to thiirene dioxides can be interpreted as following the same mechanistic pathway, the reaction was found to be second order in amine119 (which is typical for the addition of amines to olefins in appropriate solvents13 2 133), and the addition is syn. As a result, mechanisms with a cyclic-concerted addition across the carbon-carbon bond, or a stepwise addition involving two molecules of amine per one molecule of thiirene dioxide, have been proposed. 

Fig. 5. Possible mechanisms for the MMO hydroxylation step. Pathway A insertion of the oxygen atom of Q into the C-H bond B concerted addition of the C-H bond to Q followed by reductive elimination C, D homolytic attack of Q on the C-H bond E reaction of the peroxo species with substrate.

This is a general situation for thermal, concerted additions those involving Ane + 2ne systems proceed readily, e.g. the Diels-Alder reaction, whereas those involving 2ne + 2ne systems, e.g. the cyclo-dimerisation of alkenes, do not. We might, however, expect that photochemical cyclodimerisation of alkenes would be symmetry... 

The prototype concerted addition of ethene to butadiene is discussed in the next section. 

When dimethylgermylene is formed by the decomposition of 8 in the presence of excess styrene, cis- and fraws-l,l-dimethyl-3,4-diphenylgermacyclopentane forms from the apparent cycloaddition of dimethylgermylene to two alkene molecules. This is thought to occur by a stepwise mechanism where dimethylgermylene adds in a concerted fashion to styrene to yield a phenyl-substituted germacyclopropane, in the first step. In a second step, concerted addition of the germacyclopropane to a second styrene molecule has been proposed (Scheme 6). 

FIGURE 4.78 Mechanistic pathways for aromatic hydroxylation by concerted addition of oxene, pathway 1, or by stepwise addition of oxene, pathway 2. Pathways 2, 3, and 4 describe the formation of phenol that bypasses the arene oxide intermediate. 

As with an isolated double bond, epoxide formation in an aromatic ring, i.e., arene oxide formation, can occur mechanistically either by a concerted addition of oxene to form the arene oxide in a single step, pathway 1, or by a stepwise process, pathway 2 (Fig. 4.78). The stepwise process, pathway 2, would involve the initial addition of enzyme-bound Fe03+ to a specific carbon to form a tetrahedral intermediate, electron transfer from the aryl group to heme to form a carbonium ion adjacent to the oxygen adduct followed by... 

Subscripts s and a are used to indicate a supra and an antara process respectively. Suprafacial, suprafacial (s, s) approach of two polyenes is normally sterically suitable for efficient orbital overlap. The vast majority of concerted additions involves the s, s approach. 

Further supporting evidence for the occurrence of diradicals was obtained by Reich and Cram when they heated [2.2]paracyclophane with either dimethyl maleate or fumarate esters at 200 °C for 40 h in the absence of air. The cis- and trans-2,3-dicarboxymethyl[4.2]paracyclophanes 162 and 163 were formed in about equal amounts, irrespective of the configuration of the olefin employed. Other similar reactions would also suggest a radical mechanism for this reaction furthermore, a concerted addition of the olefinic double bond to 2, or to the postulated intermediate diradical 157, can be ruled out because of lack of stereospecificity of insertion. 

The mechanisms for nucleophilic GTP and electrophilic GTP are not the same. Electrophilic GTP proceeds by an associative or concerted mechanism that does not involve anionic propagating centers. Initiation involves a concerted addition of methyl trimethylsilyl dimethyl ketene acetal to monomer to form species XXV. The overall effect is to transfer... 

Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo and solvated reaction profiles, as expected. In the solvents investigated (CH2CI2 and MeOH), the most favorable mechanism is addition of peroxide anion to a fluorosilane used as starting material or formed in situ, followed by a concerted migration and dissociation of hydroxide anion. In the gas phase, and possibly in very nonpolar solvents, concerted addition-migration of H2O2 to a pentacoordinate fluorosilicate is also plausible. ... 

When hexafluoroacetone is treated with thietane (2 1) a concerted addition results in the formation of a six-membered ring (Eq. 51). Here the excited state 205 seems to favor the formation of the six-membered ring structure 207 over the corresponding thietane derivative 206. 

On the other hand, interaction between the HOMO on one ethylene and the LUMO on another ethylene is not favorable, and concerted addition to form cyclobutane would not be expected. 

Another reaction of the flavylium cation has recently been demonstrated. " It involves concerted addition of compounds possessing a polarizable double bond on the electron-deficient site C-4 and the oxygen of the 5-hydroxyl group of the anthocyanin. The new pigments thus formed, showing a second pyran ring, have been referred to as vitisins, but the term pyranoanthocyanins proposed by Lu and Foo is preferred. 

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