Reduction of Sulphones

Reduction of Sulphones.— Reduction of sulphones to sulphides is not an easy practical proposition, but di-isobutylaluminium hydride is shown to be effective.  

Cleavage and Rearrangemoit of Sulidumes.—Sulphonyl radicals formed by cleavage of sulphones and sulphonamides in toluene soluticm over Na have been studied. Methyl heptafluoro-n-propyl sulphone rather remarkably undergoes hydrolysis in dilute aqueous NaOH at 100 °C to give MeSOjH and CFjCFiCHF.  

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E. Reductions of Sulphones Using Thermolyses, Photolyses or Electrochemical Processes.962... 

Meinwald and coworkers71 studied the chemistry of naphtho[l, 8-bc]thiete and its S-oxides. The reaction of the sulphone 2 with LAH (equation 29) is of particular and direct relevance to this section since it is different from the reductions that have been discussed thus far, because the major reaction pathway is now cleavage of an S—C bond, rather than a deoxygenation of the sulphur atom. The major product (equation 29) was isolated in 65% yield two minor products accounted for a further 15% yield. One of the minor products is 1-methylthionaphthalene and this was most probably produced by an initial reduction of the strained 1,8-naphthosulphone, 2, to the thiete, which was then cleaved to the thiol and subsequently methylated. Meinwald also showed71 that the thiete was subject to cleavage by LAH as well as that both molecules were susceptible to attack and cleavage by other nucleophiles, notably methyllithium. These reactions are in fact very useful in attempts to assess a probable mechanism for the reduction of sulphones by LAH and this will be discussed at the end of this section. 

Still has also carried out mechanistic experiments9 3 from which he could deduce that the major reduction pathway is by attack of hydride ion at the sulphur atom. This conclusion was deduced from the fact that reduction with sodium borodeuteride-aluminium oxide gave a sulphoxide that had only incorporated about 25% mole equivalent of deuterium on to a methyl carbon atom bound to the sulphur atom. The mechanistic pathway for direct reduction is outlined in equation (38), whereas the pathway whereby deuterium could be incorporated is portrayed in equation (39). These reactions support the proposed mechanism for the hydride reduction of sulphones as outlined in Section III.A.l, namely that attack at sulphur by hydride ions may occur, but will be competitive with proton abstraction in cases when the attack at sulphur is not facilitated. 

The conclusion that can be drawn from this discussion of the reduction of sulphones is that reactions involving either nucleophilic or electrophilic attack are relatively difficult to... 

There are only a few examples of reductions of sulphones in acidic media. One of the earliest was a mention by Bordwell and McKellin63 (see Section III.A.l) that... 

Electrochemical reductions of sulphones have been reviewed212, and have been discussed at intervals213-215. There is evidence that the cathodic reduction reaction proceeds via a radical anion, followed by a cleavage reaction, as outlined in equation (91)212,213. 

Indirect cathodic reduction of sulphones. Redox catalysis.1014... 

Edwards two-parameter equation 549 Electrochemical oxidation of sulphides 76, 252, 253 of sulphoxides 968, 987, 1043 Electrochemical reduction of sulphones 962, 963, 1002-1041 of sulphoxides 933, 1041, 1042 Electronegativity, of the sulphur atom 584 Electronic effects 390, 484-535 Electron scavengers 892, 896 Electron spin resonance spectroscopy 874, 890-895, 1050-1055, 1082, 1083, 1090-1093... 

Since sulphones 204 are easily available compounds one would expect that they could be used as starting materials for the preparation of sulphoxides via the selective removal of one oxygen atom from the sulphonyl group (equation 112). Up to now, there is only one example reported of a direct reduction of a sulphone to a sulphoxide. The bicyclic dideuterio sulphone 205 after 24 h treatment with three-fold excess of diisobutyl aluminium hydride in boiling dichloromethane gave the corresponding sulphoxide 206 in 36% yield (equation 113). A two-step procedure for the selective reduction of sulphones to sulphoxides, which involves an initial reaction of sulphone 204 with aryldiazonium tetrafluoroborate 207 to form aryloxysulphoxonium salt 208 and its subsequent reduction (equation 114), was alluded to by Shimagaki and coworkers and... 

Classical reducing agents are known generally to be ineffective in the reduction of sulphones . Thus, although the procedure of Bouveault and Blanc has been used... 

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