PREPARATION AND REACTIVITY OF NEW BETA-NITROGEN-FUNCTIONALIZED VINYLIC ORGANOLITHIUM COMPOUNDS FROM SECONDARY ALIPHATIC ALLYLAMINES

Two new types of B-nitrogen-functionalized vinylic organolithium compounds have been prepared from secondary aliphatic allylamines through the temporary silylation of the amino group. The monoanionic intermediates 4, stable at -80 degrees C, are generated by a bromine-lithium exchange reaction and the dianionic derivatives 2, stable at room temperature, by a tin-lithium transmetalation reaction. Both types of organolithium compounds react with different electrophiles giving functionalized allylamines 7 and 10-27. Moreover, dianionic derivatives 30, 33 can be prepared directly by bromine-lithium exchange when the beta-elimination reaction of hydrogen bromide in the lithium 2-bromoallylamide is structurally hindered. Additionally, a novel type of anionic 1,3-rearrangement of a trimethylsilyl group from nitrogen to carbon is described.