Clip-and-Cleave Concept for Hydroxylation Reactions

  • ChemPubSoc Europe Logo
  • Author: Chemistry – A European Journal
  • Published Date: 09 October 2018
  • Source / Publisher: Chemistry – A European Journal/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
thumbnail image: Clip-and-Cleave Concept for Hydroxylation Reactions

Related Societies

Despite great industrial demand, the use of molecular oxygen from air as an oxidant is often problematic. Nature uses iron or copper enzymes to perform such reactions under ambient conditions. The development of synthetic compounds that mimic this activity has been a long-standing research goal.

Andrey A. Fokin, Igor Sikorsky Kiev Polytechnic Institute, Ukraine, and University of Gießen, Germany, Max C. Holthausen, University of Frankfurt am Main, Germany, Siegfried Schindler, University of Gießen, and colleagues have developed a simple "clip-and-cleave" concept for selective oxidation reactions. The team achieved efficient hydroxylations of unactivated aliphatic β-C–H bonds with high selectivity.

The synthesis involves the reaction of an aldehyde with N,N‐diethylethylenediamine to give the corresponding imine, which is used as a bidentate donor ligand forming a copper(I) complex with [Cu(CH3CN)4][CF3SO3]. The complex then reacts with dioxygen ("clip"), and as a final step, an acidic cleavage ("cleave") gives the corresponding β‐hydroxylated aldehyde.

This approach provides access to 1,2-disubstituted adamantane and diamantane derivatives that are otherwise difficult to prepare. As an extension of the concept, the amine could be immobilized, for example, on a silica matrix, which should allow the hydroxylation of aldehydes under mild conditions using only dioxygen from air.


Article Views: 1228

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

Bookmark and Share

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

CONNECT: on Facebook on Twitter on YouTube on LinkedIn Sign up for our free newsletter

A product of ChemPubSoc Europe (16 European Chemical Societies)published by Wiley-VCH