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Updated: Oct 3, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Novel Cleavage of Propargylamines by Reaction with Organolithium Compounds
José Barluenga1, Rosa-María Canteli, Josefa Flórez
1Instituto Universitario de Química Organometálica "Enrique Moles", Unidad Asociada al C.S.I.C., Universidad de Oviedo, Julián Clavería 8, 33071 Oviedo, Spain.
Abstract:
Treatment of secondary aliphatic 2-bromoallylamines with an excess of an organolithium compound led to saturated amines in which the organic group of the organolithium compound is incorporated at the alpha carbon. On the other hand, the successive reaction of the former amines with BuLi and t-BuLi between -80 degrees C and rt gave 1,3-diamines or hexahydropyrimidines depending on the reaction time. The formation of these unexpected products involves initial generation of lithium propargylamides, which subsequently undergo cleavage of the C propargylic-C acetylenic bond induced by the organolithium present in each case in the reaction medium. A mechanism which takes into account all the different reaction products has been proposed and additionally supported by successful trapping of dilithium acetylide.
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