Copper in a Metal-Free Reaction?

  • Author: Li Grundl
  • Published: 01 August 2017
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
  • Source / Publisher: Journal of the American Chemical Society/ACS Publications
  • Associated Societies: American Chemical Society (ACS), USA
thumbnail image: Copper in a Metal-Free Reaction?

Metal-free and catalyst-free reactions are becoming a new trend in organic synthesis. In some cases, metal impurities at the parts-per-million level are found to be the real catalysts. These findings can help to develop new types of high-turnover catalysis, but also show the difficulty of understanding the mechanism and identifying the true active catalyst.

Dean J. Tantillo, University of California, Davis, USA, Richmond Sarpong, University of California, Berkeley, Jason E. Hein, University of California, Merced, and colleagues have developed an apparatus to monitor reactions by ReactIR (real-time infrared spectroscopy) and Liquid chromatography-mass spectrometry (LCMS). The automated reaction sampling apparatus collects time-dependent concentration data for all chemical species during the reaction with a very high data sampling rate. This provides important information for mechanistic studies.

Such kinetic studies on a known metal-free heterocycloisomerization reaction of alkynes, combined with density functional theory (DFT) calculations, showed that the proposed mechanism was questionable. With the help of the new apparatus and additional experimental studies, the researchers revealed that trace amounts of a copper contaminant in the starting material were the real catalyst in the isomerization reaction.


Article Views: 2274

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

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