TRIANIONS BY REGIOSELECTIVE AND STEREOSELECTIVE LITHIATION OF DIALLYLAMINES AND STRUCTURALLY RELATED-COMPOUNDS - SYNTHETIC APPLICATIONS

The successive treatment of diallylamines 1 and related systems 8 and benzylallylamines 12 or 17 with alkyllithium reagents leads to several trianionic intermediates 4, 10 and 15, respectively; in the case of N ,N'-diallylethylenediamine 18 tetranionic species are obtained under t he same reaction conditions. These trianions and tetranions are charac terized by reaction with deuterium oxide to yield the corresponding de uteriated compounds 5, 11, 16 and 21. Likewise, another trianion 3a is obtained in an indirect way from diallylamine 1a via stereoselective removal of a vinylic hydrogen and further transmetallation of the viny ltin reagent 22. Models are proposed to explain the lithiation and add ition steps, which take place to give the trianions. Finally, all the lithiated intermediates react with different electrophiles (diethyl ca rbonate, carbon dioxide, dichloro-dimethylsilane and dichlorodiethylge rmanium) to give the corresponding products 27, 29, 30 and 35-44.