Highly selective electrocatalytic reduction of substituted nitrobenzenes to their aniline derivatives using a polyoxometalate redox mediator

Stergiou, A. D., Broadhurst, D. H. and Symes, M. D. (2023) Highly selective electrocatalytic reduction of substituted nitrobenzenes to their aniline derivatives using a polyoxometalate redox mediator. ACS Organic and Inorganic Au, 3(1), pp. 51-58. (doi: 10.1021/acsorginorgau.2c00047)

Abstract

Anilines and substituted anilines are used on the multi-ton scale for producing polymers, pharmaceuticals, dyes, and other important compounds. Typically, these anilines are produced from their corresponding nitrobenzene precursors by reaction with hydrogen at high temperatures. However, this route suffers from a number of drawbacks, including the requirement to handle hydrogen gas, rather harsh reaction conditions that lead to a lack of selectivity and/or toleration of certain functional groups, and questionable environmental sustainability. In light of this, routes to the reduction of nitrobenzenes to their aniline derivatives that operate at room temperature, in aqueous solvent, and without the requirement to use harsh process conditions, hydrogen gas, or sacrificial reagents could be of tremendous benefit. Herein, we report on a highly selective electrocatalytic route for the reduction of nitrobenzenes to their corresponding anilines that works in aqueous solution at room temperature and which does not require the use of hydrogen gas or sacrificial reagents. The method uses a polyoxometalate redox mediator, which reversibly accepts electrons from the cathode and reacts with the nitrobenzenes in solution to reduce them to the corresponding anilines. A variety of substituted nitroarenes are explored as substrates, including those with potentially competing reducible groups and substrates that are difficult to reduce selectively by other means. In all cases, the selectivity for the redox-mediated route is higher than that for the direct reduction of the nitroarene substrates at the electrode, suggesting that redox-mediated electrochemical nitroarene reduction is a promising avenue for the more sustainable synthesis of substituted anilines.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Symes, Professor Mark and Stergiou, Athanasios and Broadhurst, Dan
• Authors: Stergiou, A. D., Broadhurst, D. H., and Symes, M. D.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: ACS Organic and Inorganic Au
• Publisher: American Chemical Society
• ISSN: 2694-247X
• ISSN (Online): 2694-247X
• Published Online: 21 November 2022
• Copyright Holders: Copyright © 2022 The Authors
• First Published: First published in ACS Organic and Inorganic Au 3(1): 51-58
• Publisher Policy: Reproduced under a Creative Commons License
• Data DOI: 10.5525/gla.researchdata.1365

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
190559		Upgrading the small scale equipment base for early career researchers in the engineering and physical sciences	Miles Padgett	Engineering and Physical Sciences Research Council (EPSRC)	EP/K031732/1	P&S - Physics & Astronomy
301241		Ultra-Reduced Polyoxometalates as Electron-Coupled-Proton-Systems for Energy Storage	Leroy Cronin	Engineering and Physical Sciences Research Council (EPSRC)	EP/R020914/1	Chemistry
173495		Driving energetically uphill processes using metal-ligand coordination complexes	Mark Symes	The Royal Society (ROYSOC)	UF150104	Chemistry