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A group of substituted oxiranes were readily transformed to the corresponding β-hydroxyhydroperoxides (HHP) in good yields in ethereal SnCl4–H2O2 system in which SnCl4 acts as catalyst. Alternatively, treating oxiranes with SnCl4 first, followed by addition of ethereal H2O2 solution achieved primary gem-dihydroperoxides (DHP) in moderate yields. In the case of preparing DHP, SnCl4 first promoted the rearrangement of oxiranes to aldehydes, followed by condensation with hydrogen peroxide to provide DHP as final products.

We have developed a new method of N-nitrosation of various secondary and tertiary amines, amides and ureas using a mixture oftin(IV) chloride and sodium nitrate. This method leads to a selective, high-yielding and mild heterogeneous N-nitrosation by in situ generation of nitrosyl chloride (NOCl). The reaction can be carried out in several different solvents such as chloroform, dichloromethane, ethers, ethyl acetate and alcohols, at room temperature.

In the presence of SnCl 4 .5H 2 O, a mixture of thiols and tetraallyltin underwent 1,4- and 1,2-addition, respectively, with the imines derived from 3-alkynals to give (Z)-1-sulfenyl-1,5-alkadien-3-ols in good yields, wherethe hydrolysis of the intermediary imino species was found to be crucial.

In the presence of SnCl 4 .5H 2 O and acetic acid, a mixture of trimethylsilyl azide and tetraallyltin underwent 1,4- and subsequently 1,2-addition, respectively, with the α,β-unsaturated aldimines to give 1,3-hydroxy azides in good yields, where the hydrolysis of the intermediary imino species was found to be crucial.

Transmetallation of (S)-4-benzyloxy-2-pentenyl(tributyl)stannane (I) using tin(IV) chloride generates an allyltin trichloride which reacts in situ with aldehydes to give 1-substituted syn-(3Z)-5-benzyloxyhexenols with excellent stereoselectivity. With chiral aldehydes, the stereoselectivity of the reaction is dominated by the reagent, except for 2-alkoxyaldehydes which show matching and mismatching consistent with preferred Felkin-Anh diastereofacial selectivity

Allyl aryl ethers undergo facile Claisen rearrangement under mild conditions catalysed by tin(IV) chloride.