Mechanism of amination of organolithiums by alkoxyamines: use of a geometrical test for displacements on heteroatoms

Benzazetidines and Related Compounds: Synthesis and Potential

“…This amination strategy can be used to form benzazetidines and other benzo‐fused N‐heterocycles. This approach extends the already reported amination method based on displacement of an alkoxy group from an alkoxylamine by an organolithium reagent . The strategy consists of the preparation of the appropriate ( o ‐bromophenyl)alkanylmethoxylamine ( 26 a – c ) from the corresponding formyl or bromomethyl derivatives.…”

Electrophilic Amination: The Case of Nitrenoids

“…Beak et al. experimentally studied the mechanism of amination of organolithium compounds by lithium nitrenoids 73. 74 The two plausible pathways through which the amination reaction may proceed are shown in Scheme .…”

Reaction of O-benzyl-N-methylenehydroxylamine with organolithium compounds, a CH2+–NH+synthetic equivalent

“…This reagent can thus be used as a CH2+-N-OCH2Ph or CH2+-NH+ synthetic equivalent. An organolithium reagent first adds to the electrophilic carbon and subsequently, at higher temperature, to the negatively charged nitrogen intermediate (2) with concomitant displacement of the benzyloxy group providing the lithium amide intermediate (3) which in reactions with various electrophiles gives adducts of the type (4) as shown in Scheme 1.…”