Reactions of thallium(I) azide and iodine with alkenes

Abstract

The action of thallium(I) azide and iodine on some alkenes has been examined. This reagent gives different product ratios from those given by sodium azide and iodine chloride, and it differs from the latter reagent in that iodine azide cannot be preformed. Solvent incorporation occurs when thallium(I) azide–iodine is added to cyclohexene in acetonitrile. In addition to products arising from diaxial opening of α- and β-iodonium ions, products of cis-addition have been obtained from the reactions of both thallium(I) azide–iodine and sodium azide–iodine chloride on Δ²-steroids. The mode of formation of these products is discussed.