Electrosynthesis of Diaminobiaryls

  • Author: Angewandte Chemie International Edition
  • Published Date: 30 March 2017
  • Source / Publisher: Angewandte Chemie International Edition/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image: Electrosynthesis of Diaminobiaryls

2,2'-Diaminobiaryls and their derivatives are common structural motifs, for example, in organic ligands and natural products. However, their synthesis can be difficult. Nonsymmetric products, in particular, require tedious synthetic protocols. A direct oxidative treatment of aniline and its derivatives usually results in the pitch-black electrically conductive polyaniline. This reaction takes place directly on anodes.

Siegfried R. Waldvogel, University of Mainz, Germany, and colleagues have developed a direct and selective electrochemical cross-coupling of aniline derivatives. This carbon-carbon bond formation requires no leaving groups, metal catalysts, or reagents. The team used a simple beaker with two electrodes (e.g., made from glassy carbon) and a constant current. The protective groups (PG) for the amino groups are common and simple (e.g., acetyl). The selectivity for the cross-coupling is based on a solvent effect of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), which modulates the nucleophilicity of the individual coupling components, and is the key for a clean electrochemical synthesis.

The electrochemical preparation shows good yields, and the experimental set-up is very simple. A broad scope of diaryldiamines (pictured) can be accessed by this method.


Article Views: 2216

Sign in Area

Please sign in below

Additional Sign In options

Please note that to comment on an article you must be registered and logged in.
Registration is for free, you may already be registered to receive, e.g., the newsletter. When you register on this website, please ensure you view our terms and conditions. All comments are subject to moderation.

Article Comments - To add a comment please sign in

If you would like to reuse any content, in print or online, from ChemistryViews.org, please contact us first for permission. more

Follow on Facebook Follow on Twitter Follow on YouTube Follow on LinkedIn Follow on Instagram RSS Sign up for newsletters

Magazine of Chemistry Europe (16 European Chemical Societies) published by Wiley-VCH