Cyclopentadiene tropone

A secondary orbital interaction has been used to explain other puzzling features of selectivity, but, like frontier orbital theory itself, it has not stood the test of higher levels of theoretical investigation. Although still much cited, it does not appear to be the whole story, yet it remains the only simple explanation. It works for several other cycloadditions too, with the cyclopentadiene+tropone reaction favouring the extended transition structure 2.106 because the frontier orbitals have a repulsive interaction (wavy lines) between C-3, C-4, C-5 and C-6 on the tropone and C-2 and C-3 on the diene in the compressed transition structure 3.55. Similarly, the allyl anion+alkene interaction 3.56 is a model for a 1,3-dipolar cycloaddition, which has no secondary orbital interaction between the HOMO of the anion, with a node on C-2, and the LUMO of the dipolarophile, and only has a favourable interaction between the LUMO of the anion and the HOMO of the dipolarophile 3.57, which might explain the low level or absence of endo selectivity that dipolar cycloadditions show. 

Tropolone has been made from 1,2-cycloheptanedione by bromination and reduction, and by reaction with A -bromosuccinimide from cyolo-heptanone by bromination, hydrolysis, and reduction from diethyl pimelate by acyloin condensation and bromination from cyclo-heptatriene by permanganate oxidation from 3,5-dihydroxybenzoic acid by a multistep synthesis from 2,3-dimethoxybenzoic acid by a multistep synthesis from tropone by chlorination and hydrolysis, by amination with hydrazine and hydrolysis, or by photooxidation followed by reduction with thiourea from cyclopentadiene and tetra-fluoroethylene and from cyclopentadiene and dichloroketene. - ... 

Tropone (125) and the 2-substituted tropones showed a different reactivity in the cycloaddition with 2-cyclopentenone (28). Whereas tropone itself (125) and the 2-methoxytropone (126) reacted at lOkbar, giving a mixture of four and three products, respectively (Scheme 5.18), 2-hydroxy- and 2-chloro-tropone failed to react at all [43b]. Compound 127 does not have the expected dihydro-homobarrelenone framework it is probably derived from the cycloaddition of 125 and 1,4-cyclopentadien-l-ol, the enol form of 28. 

Cycloadditions, which should be allowed in the suprafacial-supra-facial mode, are known. An example is the addition of tropone to cyclopentadiene... 

All the reactions described so far have mobilised six electrons, but other numbers are possible, notably a few [8 + 2] and [6 + 4] cycloadditions involving 10 electrons in the cyclic transition structure. A conjugated system of eight electrons would normally have the two ends of the conjugated system far apart, but there are a few molecules in which the two ends are held close enough to participate in cycloadditions to a double or triple bond. Thus, the tetraene 6.17 reacts with dimethyl azodicarboxylate 6.18 to give the [8 + 2] adduct 6.19, and tropone 6.20 adds as a 6-electron component to the 4-electron component cyclopentadiene to give the adduct 6.21. 

Tropone (1) and cyclopentadiene form a single 1 1 adduct (2) in high yield when heated together at 80 Of particular note in this transformation is the production of the exo oriented adduct to the virtual exclusion of the corresponding endo product (3). This experimentally established preference for the exo mode of addition was one of the early triumphs of the Woodward-Hofimann orbital symmetry rules, which correctly predicted this stereoselectivity a year earlier. ... 

Figure 1 Frontier molecular orbitals for the cycloaddition of cyclopentadiene to tropone...

The cycloaddition of cyclopentadiene and tropone (p. 91) gives the exoadduct (181) rather than the endo-adduct (182), because the secondary interactions (Fig. 4-2lb, wavy line) of the frontier orbitals are antibonding. 

There is a special kind of site-selectivity which has been called periselectivity. When a conjugated system enters into a reaction, a cycloaddition for example, the whole of the conjugated array of electrons may be mobilized, or a large part of them, or only a small part of them. The Woodward-Hoffmann rules limit the total number of electrons (to 6, 10, 14 etc. in all-suprafacial reactions, for example), but they do not tell us which of 6 or 10 electrons would be preferred if both were feasible. Thus in the reaction of cyclopentadiene (355) and tropone (356), mentioned at the beginning of this book, there is a possibility of a Diels-Alder reaction, leading to 354, but, in fact, an equally allowed, ten-electron reaction is actually observed,121 namely the one leading to the adduct (357). The product is probably not thermodynamically much preferred to the... 

Cycloadditions. Secondary orbital interactions have been cited as an explanation for the stereochemistry of [4 + 6] cycloadditions such as that between cyclopentadiene and tropone 6.45 - > 6.46, which favours the exo transition structure 6.360. The frontier orbitals have a repulsive interaction (wavy lines) between C-3, C-4 on the tropone and C-2 on the diene (and between C-5 and C-6 on the tropone and C-3 on the diene) in the endo transition structure 6.361. However, in this reaction the exo adduct is thermodynamically favoured, the normal repulsion between filled orbitals in the endo transition structure is an adequate explanation, and the electrostatic explanation given in Section 6.5.2.4 works just as well. There is no real need to invoke secondary orbital interactions. 

Fig. 3 The EMOs of tropone and cyclopentadiene placed together for [6 + 4] and [4 + 2] cycloadditions...

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