Reductive Monoalkylation of Aromatic and Aliphatic Nitro Compounds and the Corresponding Amines with Nitriles

Abstract

[reaction: see text] A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.

Simultaneous reduction of nitro- to amino-group in the palladium-catalyzed Suzuki cross-coupling reaction

“…On the other hand, many methods have been reported for the reduction of aromatic nitro compounds to the corresponding aromatic amines, including most popular catalytic hydrogenation and metal-mediated reduction. Many valuable sources of hydrogen such as hydrazine, 3 CO/H 2 O, 4 formate, 5 NaBH 4 , 6 and amine boranes 7 have been used. Reported herein is the discovery of a novel Pd(OAc) 2 /DMF/H 2 O catalytic system for Suzuki cross-coupling reaction accompanied by the reduction of a nitro-group to an amine.…”

The one-pot process for the preparation of N-monoalkyl aromatic amines from nitroarene derivatives

“…Although excellent conversion and selectivity were achieved, the use of hydrogen gas is inaccessible to many industrial applications due to safety concerns. Recently, there have been reports on the reductive monoalkylation of aromatic and aliphatic nitro compounds with high yields [18] . The synthetic processes of N-monoalkyl compounds mostly focus on using ammonium formate as a catalytic hydrogen transfer agent and Pd/C as a hydrogen transfer catalyst at room temperature.…”

Room‐Temperature Practical Copper‐Catalyzed Amination of Aryl Iodides

“…This compound has been previously reported. [21] N-Butyl-4-methoxyaniline 3e:O btained according to the general procedure from 4-iodoanisole (234.1 mg, 1.0 mmol) and butylamine (300 mL, 3.0 mmol) at room temperature for 17 h. Upon completion, the reaction mixture was diluted with 70 mL of a1m aqueous solution of sodium hydroxide and extracted twice with 15 mL of diethyl ether.T he combined organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated under vacuum to give the desired pure product 3e as ap ale-yellow oil (150 mg, 0.83 mmol, 83 %). This compound has been previously reported.…”