Distannyl peroxides

The two principal routes to the organotin peroxides involve substitution by a peroxide nucleophile at a tin centre (equations 14-69 and 14-70), or (pericyclic) reaction of an allyltin compound with singlet oxygen (equation 14-71). Distannyl peroxides have also been prepared by the (homolytic) reaction of distannanes with triplet oxygen (equation 14-72). 

Stannyl hydroperoxides and distannyl peroxides are probably formed in homolytic chain reactions when triplet oxygen reacts with tin hydrides or distannanes, respectively, but the peroxide products are rapidly reduced by the reactants and these reactions are not useful preparatively. 

Little work has been carried out on the properties of these stannyl hydroperoxides and distannyl peroxides. Their thermal instability might suggest homolysis of the 0-0 bond, but the cleavage of the R-Sn bond which is observed might equally be regarded as re-... 

Despite their thermal instability, the distannyl peroxides have found some application in organic synthesis as a source of nucleophilic peroxide. Secondary alkyl peroxides are difficult to prepare by nucleophilic substitution by alkaline hydrogen peroxide because the products are decomposed under the alkaline conditions, but they can be obtained in fair yield by treating alkyl triflates with bis(tributyltin) peroxide.128-135... 

In contrast to these unstable stannyl hydroperoxides and distannyl peroxides, or-ganoperoxytin compounds containing the moiety SnOOR are stable and well characterised. 

A distannyl peroxide transfer reagent reacts with a,co-bis(triflates) to afford the corresponding cyclic peroxides, with the parent 1,2-dioxocane (53) obtained in 23% yield (Scheme 22) <77JA3500, 79JA4290). 

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