Nature 441, 621-623 (1 June 2006) | doi:10.1038/nature04780; Received 21 November 2005; Accepted 30 March 2006

Thermodynamic control of asymmetric amplification in amino acid catalysis

Martin Klussmann1, Hiroshi Iwamura1,3, Suju P. Mathew1, David H. Wells, Jr1,3, Urvish Pandya1, Alan Armstrong1 & Donna G. Blackmond1,2

  1. Department of Chemistry and
  2. Department of Chemical Engineering and Chemical Technology, Imperial College, London SW7 2AZ, UK
  3. †Present addresses: Mitsubishi Pharma, 14, Sunayama, Kamisu, Ibaraki 314-0255, Japan (H.I.); University of Calgary, 2500 University Drive NW, Calgary AB, T2N 1N4, Canada (D.H.W.)

Correspondence to: Donna G. Blackmond1,2 Correspondence and requests for materials should be addressed to D.G.B. (Email: d.blackmond@imperial.ac.uk).

Ever since Pasteur noticed that tartrate crystals exist in two non-superimposable forms that are mirror images of one another—as are left and right hands—the phenomenon of chirality has intrigued scientists. On the molecular level, chirality often has a profound impact on recognition and interaction events and is thus important to biochemistry and pharmacology. In chemical synthesis, much effort has been directed towards developing asymmetric synthesis strategies that yield product molecules with a significant excess of either the left-handed or right-handed enantiomer. This is usually achieved by making use of chiral auxiliaries or catalysts that influence the course of a reaction, with the enantiomeric excess (ee) of the product linearly related to the ee of the auxiliary or catalyst used. In recent years, however, an increasing number of asymmetric reactions have been documented where this relationship is nonlinear1, an effect that can lead to asymmetric amplification. Theoretical models2, 3 have long suggested that autocatalytic processes can result in kinetically controlled asymmetric amplification, a prediction that has now been verified experimentally4, 5, 6 and rationalized mechanistically7, 8, 9, 10, 11, 12, 13, 14 for an autocatalytic alkylation reaction. Here we show an alternative mechanism that gives rise to asymmetric amplification based on the equilibrium solid-liquid phase behaviour of amino acids in solution. This amplification mechanism is robust and can operate in aqueous systems, making it an appealing proposition for explaining one of the most tantalizing examples of asymmetric amplification—the development of high enantiomeric excess in biomolecules from a presumably racemic prebiotic world.


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