Download PDF
Synlett 2017; 28(01): 89-92
DOI: 10.1055/s-0036-1588912
cluster
© Georg Thieme Verlag Stuttgart · New York

Mineral-Induced Enantioenrichment of Tartaric Acid

Dragos Gherase
a   Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA   Email: blackmond@scrippps.edu
,
Robert M. Hazen
b   Department of Earth Science, George Mason University, Fairfax, VA 22040, USA
,
Ramanarayanan Krishnamurthy
a   Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA   Email: blackmond@scrippps.edu
,
Donna G. Blackmond*
a   Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA   Email: blackmond@scrippps.edu
› Author Affiliations
Further Information

Publication History

Received: 22 September 2016

Accepted after revision: 26 October 2016

Publication Date:
15 November 2016 (online)

    Permissions and Reprints All articles of this category


Abstract

Interaction of mixtures of d- and l-tartrates with dissolved gibbsite minerals produces homochiral and heterochiral dimers in a stochastic manner, providing a mechanism for enantioenrichment given a small initial imbalance. This work offers the first suggestion for a path towards the emergence of homochirality in prebiotic metabolism via the glyoxylate scenario.

Key words

enantioenrichment - prebiotic chemistry - nonlinear effects in enantiomerice excess

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588912.
  • Supporting Information
 

  • References and Notes

  • 1 Butch C, Cope ED, Pollet P, Gelbaum L, Krishnamurthy R, Liotta CL. J. Am. Chem. Soc. 2013; 135: 13440
    CrossrefPubMedSearch in Google Scholar
  • 2 Eschenmoser A. Tetrahedron 2007; 63: 12821
    CrossrefSearch in Google Scholar
  • 3 Eschenmoser A. Chem. Biodiversity 2007; 4: 554
    CrossrefPubMedSearch in Google Scholar
  • 4 Blackmond DG. Cold Spring Harbor Perspect. Biol. 2010; 2: a002147
    Search in Google Scholar
  • 5 Hein JE, Tse E, Blackmond DG. Nat. Chem. 2011; 3: 704
    CrossrefPubMedSearch in Google Scholar
  • 6 Kim H.-J, Ricardo A, Illangkoon HI, Kim MJ, Carrigan MA, Frye F, Benner SA. J. Am. Chem. Soc. 2011; 133: 9457
    CrossrefSearch in Google Scholar
  • 7 Pitsch S, Krishnamurthy R, Arrhenius G. Helv. Chim. Acta 2000; 83: 2398
    CrossrefPubMedSearch in Google Scholar
  • 8 Experiments were carried out as follows: Mineral Screening 50 mg powdered mineral were stirred in 500 μL 1 M NaOH/LiOH in D2O solution at r.t. and 1200 rpm in a 1.8 mL Eppendorf tube using a small flea stir bar (2 × 6 mm). After 30 min, dihydroxyfumaric acid (0.125 mmol, 0.25 M) and glyoxylic acid (0.125 mmol, 025 M) were added and continued stirring. After another 30 min the tube was centrifuged, and the clear solution was analyzed by 1H NMR spectroscopy. Dimer Formation from Tartaric Acid 5 mg natural gibbsite were stirred in 500 μL 0.1 M tartaric acid/1 M NaOH/1 M LiOH D2O solution at r.t. and 1200 rpm in a 1.8 mL Eppendorf tube using a small flea stir bar (2 × 6 mm). After 30 min the tube was centrifuged, and the clear solution was analyzed by 1H NMR spectroscopy. In a second set of experiments, the NaOH/LiOH solution was replaced with a 2 M LiOH solution in D2O.
  • 9 Greenwood NN, Earnshaw A. Chemistry of the Elements . 2nd ed. Butterworth-Heinemann; Oxford: 1997
    Search in Google Scholar
  • 12 Jacques J, Collet A, Wilen SH. Enantiomers, Racemates and Resolution. Krieger Publishing Company; Florida: 1991. (earlier edition: John Wiley, New York, 1981)
    Search in Google Scholar
  • 13 Klussmann M, Iwamura H, Mathew SP, Wells DH. Jr, Pandya U, Armstrong A, Blackmond DG. Nature (London, U.K.) 2006; 441: 621
    CrossrefSearch in Google Scholar