The electrophilic amination of organolithiums with methyllithium complexes of -substituted methoxyamines

Electrophilic Amination: The Case of Nitrenoids

“…This methodology was further extended to introduce N ‐alkylated amino groups (Table 6). 37, 39 The size of the substituent was shown to directly influence the amination yield. While the use of one equivalents of nitrenoid 24 a Li was sufficient to produce good yields, two equivalents of the nitrenoid resulted in higher yields (cf.…”

“…Intramolecular systems were also investigated (Scheme ) 37. 39 Substrates 80 with various intramolecular linkers were first treated with methyllithium to deprotonate the hydroxylamine and then with butyllithium. This induced lithium/bromine exchange and gave dianion 82 Li , which upon cyclisation to 83 was hydrolysed and acetylated to give cyclicproducts 81 .…”

Product Class 5: Hydroxylamines

“…However, it must be noted that stepwise alkylation with different alkylating agents affords isomeric O,N-dialkylhydroxylamines, owing to intermediate formation of O-substituted oximes and nitrones, which are either alkylated at nitrogen or oxygen. [656] Scheme 185 Synthesis of O,N-Dimethylhydroxylamine from a Quaternized Oxime [656] [657,658] or platinum, [659][660][661] or more conveniently by reaction with borohydrides, [616,[662][663][664][665][666][667][668][669][670][671][672] pyridine-borane, [72,111,349,[673][674][675][676][677] hydrosilanes, [678,679] or by hydrostannylation. [ H t-Bu 67 [662] H CH 2 CH=CH 2 51 [662] H B n 5 6 [556,662,665,666] H (CH 2 ) 2 NEt 2 16 [662] iPr Me 64 [662] Cl Me 32 [662] NO 2 Me 13 [660] Similarly, O-alkyl-N-(arylmethyl)hydroxylamines 463, which serve as building blocks for HIV-integrase inhibitors, result from the appropriate aldoximes by reduction with sodium cyanoborohydride (Scheme 187).…”

“…[672] Scheme 189 Synthesis of N-Alkyl-O-(2-hydroxy-2-phenylethyl)hydroxylamines [672] 466 ZrCl Me t-Bu 72:28 80 [672] Me 1-adamantyl 67:33 33 [672] Me (S)-CH(OH)Ph 33:67 76 [672] Pyridine-borane is an effective reagent for oxime ether reduction to give O,N-dialkylhydroxylamines. [72,349,673,674] (470), which serve as aminating agents in heterocyclic chemistry, are prepared in good yields (Scheme 190). [674] Scheme 190 N-Arylalkyl-O-methylhydroxylamines Synthesized by Reduction of Oxime Ethers [674] 191).…”

Palladium‐catalyzed reduction of nitroaromatic compounds to the corresponding anilines

“…Amines are extensively distributed in nature and display a wide range of biological activities 2–4. Several methods are available in the literature for the synthesis of amines 5–7. Some of these techniques have significant limitations regarding the safety and handling considerations 8–10.…”