Amination of Heterocyclic Compounds with O-Benzoylhydroxylamine Derivatives

Abstract

The N-amination of heterocyclic compounds 1a-k with O-benzoylhydroxylamine derivatives 5 was developed and demonstrated to be a superior alternative to existing N-amination methods. A structure-reactivity relationship study was performed on variously substituted O-benzoylhydroxylamine derivatives, leading to the discovery of the novel and more efficient aminating reagents 5h and 5i.

Inverse Electron Demand Diels–Alder Reactions of 1,2,3-Triazines: Pronounced Substituent Effects on Reactivity and Cycloaddition Scope

“…18 Deprotonation of 14 with NaH (DMF) followed by addition of monochloroamine (ClNH 2 in ether, 30 min, 23 °C) provided the N-aminopyrazole 15 in superb conversions (88–93%) that was oxidized with NaIO 4 (2 equiv, CH 2 Cl 2 –H 2 O, 2 h) at room temperature to provide 3 (81%). Although this synthesis was used to prepare most of 3 employed in our studies, we have more recently found that the N-amination of 14 to provide 15 may be accomplished even more conveniently with O -(4-nitrobenzoyl)hydroxylamine 19 (1.1 equiv of KOBu t , NMP, 20 min, 22 °C; 1.15 equiv of O -(4-nitrobenzoyl)hydroxylamine, NMP, 22 °C, 2 h, 75%). 5-Carbomethoxy-1,2,3-triazine proved to be especially reactive and was found to be sensitive to water.…”

N-Boc-O-Tosyl Hydroxylamine as a Safe and Efficient Nitrogen Source for the N-Amination of Aryl and Alkyl Amines: Electrophylic Amination

“…6 The tedious workup procedure and isolation of highly polar, water-soluble hydrazines is the major disadvantage of this method. However, N-amination of heterocycles can be achieved by O-(diphenylphosphinyl)hydroxylamine, 7 chloramine, 8 or by Oarylhydrroxylamines 9 with isolated yields ranging from 45-97%. Oxaziridine derivatives 1, 10 2, 11 and 3 4 were used as very good reagents for electrophilic amination of alkyl amines and amino acid derivatives.…”

Poly(carbazole)‐Based Copolymers Containing Deep‐Blue Chromophore for Polymer Light‐Emitting Diode Applications

“…[16][17][18][19] Synthesis of 9-(6-Bromohexyl)-9H-carbazole (1) 1,6-Dibromohexane (29.2 mL, 180 Â 10 À3 mol) was added to a mixture of carbazole (10 g, 60 Â 10 À3 mol) with N,N-dimethylformamide (DMF) (200 mL) and KOH at 0 8C. The reaction mixture was stirred at room temperature for 48 h. The organic layer was poured into water and extracted with diethyl ether.…”

“…Procedures for the Synthesis of Polymers 3,6-Dibromo-9H-carbazole, 3,6-dibromo-9-hexyl-9H-carbazole, 9-hexyl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole, and 2,2 0 -(9,9-dioctyl-9H-fluorene-2,7 0 -diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) were synthesized using a slight modification of the method reported in the literature. [16][17][18][19] Synthesis of 9-(6-Bromohexyl)-9H-carbazole (1) 1,6-Dibromohexane (29.2 mL, 180 Â 10 À3 mol) was added to a mixture of carbazole (10 g, 60 Â 10 À3 mol) with N,N-dimethylformamide (DMF) (200 mL) and KOH at 0 8C. The reaction mixture was stirred at room temperature for 48 h. The organic layer was poured into water and extracted with diethyl ether.…”

“…3,6‐Dibromo‐9H‐carbazole, 3,6‐dibromo‐9‐hexyl‐9H‐carbazole, 9‐hexyl‐3,6‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)‐9H‐carbazole, and 2,2′‐(9,9‐dioctyl‐9H‐fluorene‐2,7′‐diyl)bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane) were synthesized using a slight modification of the method reported in the literature 16–19…”