In the domain of organic chemistry, S(N)Ar substitutions represent a class of reactions of overwhelming importance, both in synthesis and in the understanding of structure-reactivity relationships, especially the role of sigma-complex intermediates. The primary factor necessary for achievement of S(N)Ar reactions is the presence of a good leaving group, which allows facile rearomatization of the ring undergoing nucleophilic attack. Consistent is the finding that the superelectrophilic chloronitrobenzofuroxans--or furazans--exhibit a very high S(N)Ar reactivity, allowing a number of C-C, C-N, C-O couplings to be achieved that are not accessible with the classical series of nitro-substituted aromatics. Of particular interest is the synthesis of a number of indoles, indolizines, pyrroles and extended pi-excessive aromatic structures like azulene substituted by superelectrophilic moieties. The remarkable driving force for the facile completion of these reactions is the 10 orders of magnitude greater reactivity of 10pi-electron-deficient heteroaromatics such as 4,6-dinitrobenzofuroxan (DNBF) than of the most reactive trinitrobenzene derivatives in sigma-adduct complexation. Among the factors that have been recognized as governing superelectrophilicity, there is the poor aromaticity of 6-membered 10pi-electron structures investigated, with a common origin for sigma-complexation and pericyclic processes. A remarkable capacity of these structures is actually to contribute to a variety of Diels-Alder reactions. As an example, the DNBF molecule formally behaves as a nitroalkene, being susceptible to act as a dienophile as well as a heterodiene. Another remarkable Diels-Alder pathway is the capacity of the 6-membered carbocyclic ring of DNBF to act as a carbodiene. Also noteworthy is the successful Diels-Alder trapping of the dinitroso intermediate associated with 1-oxide/3-oxide tautomerism of the furoxan moiety of 4-aza-6-nitrobenzofuroxan. A point of fundamental importance in taking advantage of the reactivity of superelectrophilic structures at hand has been a successful calibration of their reactivity within the electrophilicity E scale developed by Mayr to describe nucleophile-electrophile combinations in general. It has thus been established that the E parameters measuring the electrophilicity of neutral heteroaromatics lie in the same region of the E scale as a number of highly reactive cationic reagents. Besides a reactivity rather similar to that of the 4-nitrobenzenediazonium cation (vide supra), the most electrophilic neutral molecules (DNBF, DNTP, DNBZ) are as electrophilic as tropylium cations or a number of metal-coordinated carbenium ions. Furthermore, there is a remarkable link between the pK(a)(H(2)O) and E scales, as evidenced by the existence of a unique linear relationship spanning more than 20 orders of reactivity. This relationship appears as being a nice probe to predict the feasibility of S(N)Ar substitutions and related sigma-complexation processes. Also revealing in terms of feasibility of the rea...
