9. Dynamic Approaches towards Catalyst Discovery

  1. Peter I. Dalko
  1. Patrizia Galzerano,
  2. Giulio Gasparini,
  3. Marta Dal Molin and
  4. Leonard J. Prins

Published Online: 23 AUG 2013

DOI: 10.1002/9783527658862.ch9

Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications

Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications

How to Cite

Galzerano, P., Gasparini, G., Dal Molin, M. and Prins, L. J. (2013) Dynamic Approaches towards Catalyst Discovery, in Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications (ed P. I. Dalko), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527658862.ch9

Editor Information

  1. Université Paris-Descartes, PRES Sorbonne Paris Cité, CNRS, 45, rue des Saints-Pères, 75270 Paris Cedex 06, France

Publication History

  1. Published Online: 23 AUG 2013
  2. Published Print: 23 OCT 2013

ISBN Information

Print ISBN: 9783527332366

Online ISBN: 9783527658862



  • dynamic combinatorial chemistry;
  • molecular capsules;
  • self-assembly;
  • supramolecular catalysis;
  • transition state recognition


This chapter describes approaches towards organocatalyst discovery relying on dynamic chemistry, that is, chemistry relying on reversible bond formation. The use of dynamic chemistry is an attractive option as it allows for self-assembly and self-selection processes. Self-assembly implies that catalyst formation occurs spontaneously upon mixing subunits equipped with complementary recognition elements. It will be shown that this permits the straightforward formation of large catalyst libraries simply by mixing a limited number of subcomponents. Typically, the activity of the catalytic complex is higher in terms of activity and selectivity compared to the separate subunits. Self-assembly can also be used in a more indirect manner by creating molecular cages able to encapsulate reagents. This is a highly attractive strategy for several reasons. Encapsulation increases the effective concentration of reagents and fixes their relative orientation depending on the geometry of the cage. Additionally, the interior of the cage represents a local chemical environment that is different from the bulk, which can be beneficial for the chemical reaction occurring in the cage. The final part of the chapter is dedicated to examples in which catalyst discovery occurs by means of self-selection processes. This approach relies on the exposure of a dynamic library of potential catalysts to a transition state analog of a chemical reaction. This causes a shift in the thermodynamic composition of the library in favor of the catalyst that can most strongly interact with the transition state. The advantage is that it relies on self-selection and that, in principle, no a priori knowledge about the nature of the interaction between catalyst and transition state is required.