Superoxides reaction with alkyl sulfonates

The reactions of alkyl sulfonates with superoxide ion and with nitrite ion directly afford the corresponding inverted alcohols. - Although displacement by superoxide ion has been successfully utilized in prostaglandin chemistry, elimination again takes place to some extent, depending on the structures of the substrates. In the reaction with nitrite ion, ketone and nitroalkane are also formed. The inversion of cyclopentanol derivatives via tosylates has been studied by the use of various methods involving displacement by benzoate, nitrite ion and superoxide ion as well as the diethyl azodicarboxylate (DEAD)-PhsP procedure, where varied amounts of elimination products are invariably formed. ... 

The reaction of primary alkyl bromides or sulfonate esters with potassium superoxide solubilized in benzene gives dialkyl peroxides, ROOR, as the major product. Significant amounts of alcohols and olefins are also formed. If the reaction is carried out in DMSO or DMSO-DMF, primary alcohols are formed very rapidly with inversion of configuration. Catalytic amounts of a crown ether are sufficient, but use of 1-2 eq. leads to a more rapid reaction. Secondary alcohols can be obtained, often in high yield, by this displacement reaction, but elimination predominates with tertiary substrates. This Sn2 reaction has been... 

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