7.22 Enzyme Catalytic Promiscuity: Expanding the Catalytic Action of Enzymes to New Reactions

R. J. Kazlauskas, U. T. Bornscheuer

Research output: Chapter in Book/Report/Conference proceedingChapter

10 Scopus citations


The use of enzymes as catalysts for organic synthesis requires that they catalyze nonbiochemical reactions. This promiscuity can be an ability to accept substrates beyond their natural biochemical substrates (substrate promiscuity) or an ability to catalyze new reactions (catalytic promiscuity). This chapter focuses on this second type of promiscuity. Catalytically promiscuous reactions are additional abilities of enzymes beyond their normal reaction. The promiscuous reactions share mechanistic steps with the normal reaction. Chemists can use catalytically promiscuous reactions for synthesis. Protein engineering can improve the existing catalytically promiscuous reaction and, by adding new mechanistic steps, create new catalytic promiscuity. This chapter reviews examples of catalytic promiscuity, organized by reaction type, with an emphasis on stereoselective carbon-carbon bond forming reactions such as aldol and Michael additions.

Original languageEnglish (US)
Title of host publicationComprehensive Chirality
PublisherElsevier Ltd
Number of pages16
ISBN (Print)9780080951683
StatePublished - Sep 2012

Bibliographical note

Funding Information:
U T Bornscheuer thanks the German Research Foundation (DFG, Grant) and R J Kazlauskas thanks the US National Science Foundation for financial support.

Copyright 2014 Elsevier B.V., All rights reserved.


  • Acyloin condensation
  • Alpha/beta-unsaturated carbonyl compounds
  • Catalytic promiscuity
  • Decarboxylases
  • Glycosynthases
  • Hydrolases
  • Michael-type addition
  • Nitroaldol addition
  • Polyene cyclization
  • Pyridoxal-dependent aldolases
  • Serine hydrolases


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