Mild Hydrogenation of Amides to Amines over a Platinum‐Vanadium Bimetallic Catalyst

Abstract

Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H at 70 °C or 5 bar H at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.

The Catalytic Reduction of Carboxylic Acid Derivatives and CO2 by Metal Nanoparticles on Lewis‐Acidic Supports

“…Early heterogeneous catalysts such as Cu−Cr oxides, activated Co and Ni catalysts, and Re catalysts selectivity catalyze the hydrodeoxygenation of amides to amines under harsh conditions (20–30 MPa H 2 , ∼250 °C) ,,,. More recently, catalysts that combine group 8–10 with group 5–7 metals have been found to be effective, which has raised substantial interest ,,,. For instance, Fuchikami et al .…”

Palladium doping of In2O3 towards a general and selective catalytic hydrogenation of amides to amines and alcohols

“…With this aim, a large screening of bi-and trimetallic systems was also performed, which allowed the identification of a relatively active catalyst based on Pt-Re-In supported on silica (or carbon). 29 Nevertheless, the most significant breakthrough to date has been recently reported, almost at the same time, by the groups led by Kaneda and Shimizu, who applied V-decorated Pt nanoparticles impregnated on hydroxyapatite (HAP) 30 and Re-loaded TiO 2 , 31 respectively, as catalysts for the hydrogenation of amides via C-O bond cleavage (Path A), while inhibiting arene hydrogenation.…”

Recent Advances in Amide Reductions

“…22 In 2017, Kaneda disclosed a vanadium-platinum bimetallic catalyst impregnated on hydroxyapatite (HAP) that enabled hydrogenation of amides at a temperature as low as 25 °C (Scheme 11). 24,25 These conditions exhibited high selectivity for the C=O cleavage and could be applied to a wide scope of substrates (secondary and tertiary amides, lactams), being only limited in the cases of challenging primary amides (Scheme 11). The catalyst could be reused ten times with no loss of reactivity and several experiments were conducted under only one atmosphere of hydrogen.…”