Volume 247, 2023

Electroorganic synthesis in aqueous solution via generation of strongly oxidizing and reducing intermediates

Abstract

Water is the ideal green solvent for organic electrosynthesis. However, a majority of electroorganic processes require potentials that lie beyond the electrochemical window for water. In general, water oxidation and reduction lead to poor synthetic yields and selectivity or altogether prohibit carrying out a desired reaction. Herein, we report several electroorganic reactions in water using synthetic strategies referred to as reductive oxidation and oxidative reduction. Reductive oxidation involves the homogeneous reduction of peroxydisulfate (S2O82−) via electrogenerated Ru(NH3)62+ at potential of −0.2 V vs. Ag/AgCl (3.5 M KCl) to form the highly oxidizing sulfate radical anion (E0′ (SO4˙/SO42−) = 2.21 V vs. Ag/AgCl), which is capable of oxidizing species beyond the water oxidation potential. Electrochemically generated SO4˙ then efficiently abstracts a hydrogen atom from a variety of organic compounds such as benzyl alcohol and toluene to yield product in water. The reverse analogue of reductive oxidation is oxidative reduction. In this case, the homogeneous oxidation of oxalate (C2O42−) by electrochemically generated Ru(bpy)33+ produces the strongly reducing carbon dioxide radical anion (E0′ (CO2˙/CO2) = −2.1 V vs. Ag/AgCl), which can reduce species at potential beyond the water or proton reduction potential. In preliminary studies, the CO2˙ has been used to homogeneously reduce the C–Br moiety belonging to benzyl bromide at an oxidizing potential in aqueous solution.

Graphical abstract: Electroorganic synthesis in aqueous solution via generation of strongly oxidizing and reducing intermediates

Associated articles

Additions and corrections

Article information

Article type
Paper
Submitted
14 Mar 2023
Accepted
06 Apr 2023
First published
24 Apr 2023

Faraday Discuss., 2023,247, 195-208

Author version available

Electroorganic synthesis in aqueous solution via generation of strongly oxidizing and reducing intermediates

S. Hosseini, J. A. Beeler, M. S. Sanford and H. S. White, Faraday Discuss., 2023, 247, 195 DOI: 10.1039/D3FD00067B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements