Stannyl hydroperoxides

Some examples of stannyl hydroperoxides and peroxides are included in Table 14-7. 

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-... 

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

Nitrile oxides were also readily generated by reaction of aldoximes 172 with icri-butyl hydroperoxide and bis(tributyltin) oxide. The reaction proceeded nnder mild conditions, in which 0-stannylated aldoximes 173 were the key intermediates. This reaction system was applicable to the one-pot synthesis of isoxazoline 174 or isoxazole 175 derivatives... 

Allylstannanes are converted to hydroperoxides with a vinylic stannyl group. The reaction is stereoselective. 

The products are formed in good chemical yields and high diastereoselectivity, analogous to the Sharpless-method from acyclic substrates, R S (unHke, /)-products 32 were formed preferentially. The allylic hydroperoxides obtained from the photooxygenation of vmyKc silanes or stannanes are readily dehydrated to a,(3-unsaturated carbonyl products with a silyl or stannyl group at the a carbon (Scheme 18). 

Adam, W. and Klug, R, P-Stannyl allylic alcohols through photooxygenation (Schenck reaction) of vinylstannanes and reduction of the resulting aUyhc hydroperoxides synthesis and selected transformations,/. Org. Chem., 59, 2695, 1994. 

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