Synthesis and Properties of Glycolaldehyde Di- and Triphosphate

Anthony J. Lawrence; John D. Sutherland

doi:10.1055/s-2002-19325

LETTER

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;

Abstract

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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

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Referenzen

References

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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), [M^3- + 2 H⁺]^-; MS (ES-, CV -25 V): m/z (%) = 237(100), [M^3- + 2 H⁺]^-), 219(100), [M^3- + 2 H⁺ - H₂O]^-); MS (ES-, CV -35 V): m/z (%) = 219(100), [M^3- + 2 H⁺ - H₂O]^-).

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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), [M^4- + 2 H⁺ + Na⁺ - H₂O]^-), 299(5) [M^4- + 3 H⁺ - H₂O]^-).

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