Sustainable Hydrogenation of Nitroarenes to Anilines with Highly Active in‐situ Generated Copper Nanoparticles

Abstract

Metal nanoparticles (NPs) are usually stabilized by a capping agent, a surfactant, or a support material, to maintain their integrity. However, these strategies can impact their intrinsic catalytic activity. Here, we demonstrate that the in‐situ formation of copper NPs (Cu0NPs) upon the reduction of the earth‐abundant Jacquesdietrichite mineral with ammonia borane (NH3BH3, AB) can provide an alternative solution for stability issues. During the formation of Cu0NPs, hydrogen gas is released from AB, and utilized for the reduction of nitroarenes to their corresponding anilines, at room temperature and under ambient pressure. After the nitroarene‐to‐aniline conversion is completed, regeneration of the mineral occurs upon the exposure of Cu0NPs to air. Thus, the hydrogenation reaction can be performed multiple times without the loss of the Cu0NPs’ activity. As a proof‐of‐concept, the hydrogenation of drug molecules “flutamide” and “nimesulide” was also performed and their corresponding amino‐compounds were isolated in high selectivity and yield.

A review on the synthesis and applications of sustainable copper-based nanomaterials

“…18a and b). 302 The synthetic mineral consisted of cuboid-shaped single crystals, indicating the formation of Cu 0 NPs before and after the reaction, while the size of the Cu 0 NPs was in the range of 20–40 nm after the reaction was complete. 302 The in situ -prepared Cu 0 NPs demonstrated catalytic activity for the hydrogenation of nitrobenzene to aniline in a mixture of MeOH and H 2 O at 25 °C (Fig.…”

Unraveling Transfer Hydrogenation Mechanisms by Ammonia Borane to Alkenes over Self-Healing Copper Nanoparticles: The Complementary Role of N–H Bond, Surface, and Solvent

“…Interestingly, AB is selectively decomposed by SION-X to H 2 , without borane formation. 53,54 Unlike other copper sources, this mineral can be reformed quantitatively after the transfer hydrogenation reaction by exposure of the solution to the air. The mechanism behind the self-healing properties of these CuNPs is discussed in refs 53 and 54.…”

Three-Dimensional Printing Multi-Drug Delivery Core/Shell Fiber Systems with Designed Release Capability

“…The results showed that the CFSs loading DOX and PXT had a better ability to kill cancer cells. The synergistic effect of DOX and PXT exhibited excellent antitumor efficiency toward various solid tumors, such as breast cancer, by blocking off cells in the G2 m phase [ 26 , 27 ]. Furthermore, polydopamine or methacrylic acid copolymer-modified polycaprolactone (MAC−PCL) could also be introduced into this system to achieve NIR-triggered or pH-responsive drug release.…”