Trianions by regio- and stereo-selective lithiation of diallylamines and structurally related compounds: synthetic applications

Abstract

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 the same reaction conditions. These trianions and tetranions are characterized by reaction with deuterium oxide to yield the corresponding deuteriated compounds 5, 11, 16 and 21. Likewise, another trianion 3a is obtained in an indirect way from diallylamine 1avia stereoselective removal of a vinylic hydrogen and further transmetallation of the vinyltin reagent 22. Models are proposed to explain the lithiation and addition steps, which take place to give the trianions. Finally, all the lithiated intermediates react with different electrophiles (diethyl carbonate, carbon dioxide, dichlorodimethylsilane and dichlorodiethylgermanium) to give the corresponding products 27, 29, 30 and 35–44.