Divergent Enzyme Catalysis for Acyloins

  • Author: Pamela Alsabeh
  • Published Date: 07 September 2016
  • Source / Publisher: Chemistry – A European Journal/Wiley-VCH
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
thumbnail image: Divergent Enzyme Catalysis for Acyloins

Related Societies

2-Hydroxy ketones, also known as acyloins, are valuable chiral compounds in asymmetric synthesis. Benzoin reactions, a type of catalytic asymmetric C–C bond formation, are used to form 2-hydroxy ketones. In nature, thiamine diphosphate (ThDP)-dependent enzymes can catalyze the formation of 2-hydroxy ketones. In the cross-benzoin reaction of an aliphatic and an aromatic aldehyde, several different products can be formed (example pictured). Certain isomers of these products are difficult to access in a regio- and stereoselective manner.

Michael Müller, University of Freiburg, Germany, and colleagues have found a selective catalytic asymmetric pathway to each 2-hydroxy ketone isomer among all possible products using divergent catalysis. They used ThDP-dependent enzymes as catalysts for an aliphatic-aromatic cross-benzoin reaction, and investigated the scope and limitations of their approach.

The researchers used a set of two R-selective and two S-selective ThDP-dependent enzymes. They achieved the divergent selective synthesis of both R- and S-isomers of 2-hydroxypropiophenone and phenylacetylcarbinol, as well as derivatives thereof. By choosing the appropriate enzyme, the team was able to form the desired product in a regio- and stereoselective manner.

This divergent catalytic system can, in principle, provide access to every desired 2-hydroxy ketone isomer selectively, even the thermodynamically less stable one, under kinetically controlled conditions.


Article Views: 2174

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


ChemistryViews.org on Facebook

ChemistryViews.org on Twitter ChemistryViews.org on YouTube ChemistryViews.org on LinkedIn Sign up for our free newsletter

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