Download PDF
Synlett 2002(1): 0170-0172
DOI: 10.1055/s-2002-19325
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Properties of Glycolaldehyde Di- and Triphosphate

Anthony J. Lawrence, John D. Sutherland*
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK
Fax: +44(161)2754939; e-Mail: john.sutherland@man.ac.uk;
Further Information

Publication History

Received 29 October 2001
Publication Date:
01 February 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

Use of photolabile acetal protecting groups enables the synthesis of glycolaldehyde di- and triphosphate 4 and 5, which undergo enolisation at significantly lower pH values than glycolaldehyde phosphate 1. At pH > 10, 5 is converted to 1 and inorganic pyrophosphate.

Key words

aldehydes - bioorganic chemistry - ozonolysis - phosphorylations - photochemistry

    References

  • 1 Müller D. Pitsch S. Kittaka A. Wagner E. Wintner CE. Eschenmoser A. Helv. Chim. Acta  1990,  73:  1410 
    CrossrefGoogle Scholar
  • 2 Krishnamurthy R. Arrhenius G. Eschenmoser A. Origins of Life and Evolution of the Biosphere  1999,  29:  333 
    CrossrefGoogle Scholar
  • 3 Krishnamurthy R. Pitsch S. Arrhenius G. Origins of Life and Evolution of the Biosphere  1999,  29:  139 
    CrossrefGoogle Scholar
  • 4 Dixit VM. Laskovics FM. Noall WI. Poulter CD. J. Org. Chem.  1981,  46:  1969 
    Google Scholar
  • 6 For related chemistry involving acylation of α-methoxy-hydroperoxides by anhydrides see: Schreiber SL. Liew W.-F. Tetrahedron Lett.  1983,  24:  2363 
    CrossrefGoogle Scholar
  • 7 Tsunoda T. Suzuki M. Noyori R. Tetrahedron Lett.  1980,  21:  1357 
    CrossrefGoogle Scholar
  • 8 Gravel D. Murray S. Ladouceur G. J. Chem. Soc., Chem. Commun.  1985,  1828 
    CrossrefGoogle Scholar
  • 9 Pitsch S. Helv. Chim. Acta  1997,  80:  2286 
    CrossrefGoogle Scholar
  • 11 Taylor SD. Kluger R. J. Am. Chem. Soc.  1993,  115:  867 
    CrossrefGoogle Scholar
5

Compound 4: 1H NMR (500 MHz, D2O, pD 8.0): δ = 3.79 (2 H, dd, J = 4.5, J = 6.5, CH2), 5.04 (1 H, t, J = 4.5, CH); 13C NMR (125 MHz, D2O, pD 8.0): δ = 67.9 (d, J = 5.0), 88.5 (d, J = 9.0); 31P NMR (83 MHz, 10 mM EDTA in D2O, pD 8.0): δ = -9.25 (d, J = 22.0), -5.06 (d, J = 22.0); MS (ES-, CV -15 V): m/z (%) = 237(100), [M3- + 2 H+]-; MS (ES-, CV -25 V): m/z (%) = 237(100), [M3- + 2 H+]-), 219(100), [M3- + 2 H+ - H2O]-); MS (ES-, CV -35 V): m/z (%) = 219(100), [M3- + 2 H+ - H2O]-).

10

Compound 5: 1H NMR (300 MHz, D2O, pD 8.5): δ = 3.78 (2 H, dd, J = 4.5, J = 7.5, CH2), 5.04 (1 H, t, J = 4.5, CH); 13C NMR (75 MHz, D2O, pD 8.5): δ = 68.1 (d, J = 5.5), 88.3(brs); 31P NMR (83 MHz, 1 mM EDTA in D2O, pD 9.0): δ = -20.85 (t, J = 19.5), -9.70 (d, J = 19.5), -4.95 (d, J = 19.5); MS (ES-, CV -35V): m/z (%) = 321(20), [M4- + 2 H+ + Na+ - H2O]-), 299(5) [M4- + 3 H+ - H2O]-).