Radical sulfonyl

TABLE 9. Bond energies in sulfoxides and sulfones, and enthalpies of formation of sulfinyl and sulfonyl radicals... 

Arising from studies of the photochemistry of benzenesulfonyl systems, extensive ab initio MO calculations have been made for various sulfonyl radicals and related species253. The STO-3G basis set, which includes d-type polarization functions on second-row atoms, was used. The inclusion of d orbitals on sulfur was found to be very... 

Gilbert and co workers42 found the same behavior of OH radicals with other aliphatic sulfoxides. In many of these cases the OH adduct is decomposed to the sulfonyl radical. 

Sulfonyl radicals are often represented simply as XS02 where the sulfur atom is understood to be bonded to two oxygens as well as to X the moiety X may be an alkyl, aryl, amino or alkoxy group. The unpaired electron does not reside on one particular atom but rather it extends over all atoms of the S02 group. It should be noted that in recent literature some authors refer to alkanethiyl peroxyl radicals, the adduct of alkanethiyl (RS ) to molecular oxygen, as RS02 rather than RSOO and the fact has already caused some inconvenience. 

Sulfonyl radicals are highly reactive transient species despite their short lifetime, they figure in a wide variety of organosulfur reactions, some of which are of great synthetic... 

A few words about the pattern of organization of this chapter. The theoretical studies are included in Section II. In Section VII some interesting chain reactions involving sulfonyl radicals are discussed, although often one of the propagation steps is treated earlier in Section IV or V. Finally, some general concepts of free radical chemistry are introduced at appropriate points throughout the review without any reference. 

The ESR spectra of a large variety of sulfonyl radicals have been obtained photolytically in liquid phase over a wide range of temperature. Some selected data are summarized in Table 2. The magnitudes of hyperfine splittings and the observations of line broadening resulting from restricted rotation about the C—S bond have been used successfully in conjunction with INDO SCF MO calculations to elucidate both structure and conformational properties. Thus the spin distribution in these species is typical of (T-radicals with a pyramidal center at sulfur and in accord with the solid-state ESR data. 

TABLE 1. Characteristics of the orbital containing the unpaired electron in sulfonyl radicals calculated from 33S splittings... 

The thiophene-2-sulfonyl radicals without substituents at position 3 exhibit rapid rotation about the C—S bond in the ESR time scale, while the 3-bromo-substituted ones demonstrate a marked conformational preference which has been interpreted in terms of a re-type conjugated structure similar to 3 (cf. entries 10 and 11 in Table 2)10. Calculations... 

TABLE 2. ESR spectra of a selected number of sulfonyl radicals at temperatures between 170 and 200 K... 

Typical values of g for some sulfonyl radicals are also listed in Table 2. Two main features stand out from these data. First, there is a decrease in the g-value as the electronegativity of the substituents increases, that is, MeSOj (2.0049), Me2NS02 (2.0036), MeOSOj (2.0032) and FSOj (2.0026), and second, there is an increase in the g-value when introducing atoms characterized by large spin-orbit couplings in positions of significant spin density of the radical (cf., for example, entries 7 and 9 as well as 10 and 11 in Table 2). 

TABLE 3. Electronic spectral parameters of sulfonyl radicals... 

Sulfones are thermally very stable compounds, diaryl derivatives being more stable than alkyl aryl sulfones which, in turn, are more stable than dialkyl sulfones allyl and benzyl substituents facilitate the homolysis by lowering the C—S bond dissociation energy17. Arylazo aryl sulfones, on heating in neutral or weakly basic media at 100°C, yield an aryl and arenesulfonyl radical pair via a reversible one-bond fission followed by dediazoni-ation of the aryldiazenyl radical (see Scheme 2 below)20. However, photolysis provides a relatively easy method for generating sulfonyl radicals from compounds containing the S02 moiety. 

The most common way to generate sulfonyl radicals for spectroscopic studies has been the photolysis of solutions containing di-t-butyl peroxide, triethylsilane and the corresponding sulfonyl chloride in a variety of solvents (equations 4-6). The slowest step in this sequence is the reaction between t-butoxyl radicals and triethylsilane (ks = 5.3 x 106m 1s-1)26 since that for chlorine abstraction (equation 6) is extremely efficient (cf. Table 4). 

In pulse radiolysis studies, sulfonyl radicals have normally been generated by dissociative electron capture using sulfonyl chlorides as substrates, namely15. 

The key step in the radical chain decomposition of alkanesulfonyl halides as well as in the adduct formation of sulfonyl halides with alkenes (vide infra) is equation 8 in which the R radical abstracts an X atom from the sulfonyl halide to regenerate a sulfonyl radical. 

An important route to sulfonyl radicals is the reaction of a radical with sulfur dioxide ... 

One of the peculiar features of sulfonyl radicals is the a-scission process, namely... 

The rapid desulfonylation of PhCH2SO 2 has been used successfully as a probe for laser flash photolytic investigations of various reactions generating sulfonyl radicals from sulfonyl halides26,28. 

Intramolecular cyclization of sulfonyl radicals is almost absent from literature. The fact that free radical cyclization has been the subject of a large number of studies and applications in the last decade in organic chemistry48 and that sulfonyl radicals add quickly to multiple bonds (vide infra) makes cyclization of sulfonyl radicals a rather attractive area. Recently, Johnson and Derenne49 studied the reaction of 6-methylhept-5-en-2-ylcobaloxime(III) with sulfur dioxide and, based on the product analysis, they suggested reaction 15 to be an intermediate step. 

Correa and Waters50 also proposed a mechanistic scheme where the key step of the overall reaction involves the recombination of sulfonyl radicals to form an intermediate with an O—S bond, the decomposition of which yields a sulfinyl radical (ArSO ) and an oxygen-centered radical ArS020 Later this suggestion was further strengthened on the basis of ESR studies51 and thanks to the elucidation of the electronic structure of sulfonyl radicals. However, it seems to the author that the available literature data point to an overall mechanism for equation 17 more complex that the one suggested50 (cf., for... 

The product distribution derived from the disproportionation of sulfonyl radicals is expected to be dependent on the conditions under which the reaction is being carried out thus, in hydrogen donor solvents, the formation of ArS020H should be important while at higher temperatures the formation of an aryl radical, namely... 

Absolute rate constants for the addition of a sulfonyl radical to multiple bonds are absent from the literature. However, there are some relative kinetic data. Correa and... 

Waters61 have measured relative rates of p-toluenesulfonyl radical addition to substituted styrenes, deducing from the value of p + = — 0.50 in the Hammett plot that the sulfonyl radical has an electrophilic character (equation 21). Further indications that sulfonyl radicals are strongly electrophilic have been obtained by Takahara and coworkers62, who measured relative reactivities for the addition reactions of benzenesulfonyl radicals to various vinyl monomers and plotted rate constants versus Hammett s Alfrey-Price s e values these relative rates are spread over a wide range, for example, acrylonitrile (0.006), methyl methacrylate (0.08), styrene (1.00) and a-methylstyrene (3.21). The relative rates for the addition reaction of p-methylstyrene to styrene towards methane- and p-substituted benzenesulfonyl radicals are almost the same in accord with their type structure discussed earlier in this chapter. 

There is clear evidence that the addition of a sulfonyl radical to an olefin is a reversible reaction. This has been demonstrated for the case of but-2-ene, where cis-trans isomerization of the olefin accompanies addition63,64. Furthermore, 18a and 18b radicals generated by the reaction of Bu3Sn with erythro- and tfireo-2-bromo-3-(phenylsulfonyl)butane, respectively, eliminate benzenesulfonyl radicals to some extent, even at — 67 °C, to form 2-butenes in a non-stereospecific manner, providing also indication that the rotation about the central C—C bond is faster than the /1-cleavage process65. 

In principle two possible pathways may exist for the addition of sulfonyl radicals to olefmic double bonds, that is, attack by either the sulfur or an oxygen atom, as in sulfonyl radicals the spin density is almost equally divided between sulfur and the two oxygens, namely... 

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