A modification of the Sheverdina-Kocheshkov amination: the use of methoxyamine-methyl lithium as a convenient synthetic equivalent for NH2+

A Homologous Series of O‐ and N‐Functionalized 2,2‐Difluoro1,3‐benzodioxoles: an Exercise in Organometallic Methodology

“…Using lithium methoxyamide,18−20 (2,2‐difluoro‐1,3‐benzodioxol‐4‐yl)lithium could be directly converted into the aniline 3a although only in moderate yield (40%). The more lengthy route through the ketone 10 (68% from the carboxylic acid 1a ), condensation with hydroxylamine and Beckmann rearrangement of the resulting oxime 18 (84%) proved to be more expedient (83% of 3a in the last step).…”

Electrophilic Amination: The Case of Nitrenoids

“…As the initial formation of metallated species from methoxyamine was apparent, Wakefield suggested to use expandable lithium/magnesium reagent to deprotonate the nitrenoid precursors prior to use 83. In 1982, Beak and Kokko reported successful generation of lithium nitrenoid 23 Li from methoxyamine and methyllithium in diethyl ether, which was subsequently used for amination of a wide range of organometallic reagents 36. While amination of organolithium and organocopper was successful (see later sections for details), that of Grignard reagents was far less efficient (Scheme ).…”

“…In 1982, Beak and Kokko demonstrated that lithium nitrenoid 23 Li , pre‐formed from methoxyamine and methyllithium in diethyl ether was an efficient reagent for amination of organolithium compounds (Table 5). 36 Deprotonation of methoxyamine with n BuLi or PhLi instead of MeLi or use of solvents other than diethyl ether to generate the title nitrenoid was shown to be less efficient. The outcomes of trapping experiments confirmed that both n BuLi and PhLi reacted rapidly during the deprotonation step with the freshly formed nitrenoid species and were largely aminated prior to addition of the amination substrate.…”

End-capping of polystyrene by aliphatic primary amine by derivatization of precursor hydroxyl end group

“…For instance, molecules containing protected primary amine must be used as either initiator or terminating agent. A series of papers have reported on this strategy as compiled in Table I 4–12.…”