General synthesis of primary amines via reductive amination employing a reusable nickel catalyst

Abstract

Reusable catalysts based on earth-abundant metals with a broad applicability in organic synthesis are a key to a more sustainable production of fine chemicals, pharmaceuticals and agrochemicals. Herein, we report on a nanostructured nickel catalyst for the general and selective synthesis of primary amines via reductive amination, employing ammonia dissolved in water. Our catalyst, which operates at low temperature and pressure, is highly active, reusable and easy to handle. The synthesis from a specific nickel complex and γ-Al2O3 is straightforward, with the ligand–metal combination of this complex being crucial. Aldehydes (including purely aliphatic ones), aryl–alkyl, dialkyl and diaryl ketones can all be converted smoothly into primary amines. In addition, the amination of pharmaceuticals, bioactive compounds and natural products is demonstrated. Many functional groups—including hydrogenation-sensitive examples—are tolerated. We expect that our findings will inspire others to develop reusable and nanostructured earth-abundant metal catalysts for complex organic transformations.