Stereochemistry of the acyl dihydroxyacetone phosphate acyl exchange reaction

S. J. Friedberg, N. Satsangi, Susan E Weintraub

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The fatty acid of acyl dihydroxyacetone phosphate can be exchanged enzymatically for another fatty acid. It has been shown that this reaction proceeds by cleavage of the oxygen bound to C-1 of the dihydroxyacetone phosphate (DHAP) moiety rather than by the more common cleavage at the acyl to oxygen bond. In the present study, the stereochemistry of this reaction was defined further; using deuterated substrates and fast atom bombardment-mass spectrometry, it was shown that the fatty acid exchange involves the stereospecific labilization of the pro-R hydrogen at C-1 of the DHAP moiety of acyl DHAP. The mechanism of ether bond formation, in which acyl DHAP is converted to O-alkyl DHAP, also proceeds via labilization of the pro-R hydrogen and cleavage of the fatty acid at the C-1 to oxygen bond. In addition, other workers have provided evidence that the enzyme responsible for the exchange reaction is O-alkyl DHAP synthetase. Therefore, the present results support the hypothesis that the acyl exchange is the reverse reaction of the first step O-alkyl DHAP synthesis; in both of these reactions the pro-R hydrogen of C-1 of the DHAP moiety of acyl DHAP and the fatty acid moiety are labilized with cleavage of the fatty acid at the DHAP C-1 to oxygen bond.

Original languageEnglish (US)
Pages (from-to)259-266
Number of pages8
JournalJournal of Lipid Research
Volume32
Issue number2
StatePublished - 1991

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Dihydroxyacetone Phosphate
Stereochemistry
Fatty Acids
Oxygen
Hydrogen
Fast Atom Bombardment Mass Spectrometry
Ligases
Ether
Mass spectrometry

Keywords

  • enzymology
  • ether bond formation
  • ether lipids
  • fast atom bombardment-mass spectrometry
  • glyceryl ethers
  • O-alkyl DHAP
  • stereochemistry

ASJC Scopus subject areas

  • Endocrinology

Cite this

Stereochemistry of the acyl dihydroxyacetone phosphate acyl exchange reaction. / Friedberg, S. J.; Satsangi, N.; Weintraub, Susan E.

In: Journal of Lipid Research, Vol. 32, No. 2, 1991, p. 259-266.

Research output: Contribution to journalArticle

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AB - The fatty acid of acyl dihydroxyacetone phosphate can be exchanged enzymatically for another fatty acid. It has been shown that this reaction proceeds by cleavage of the oxygen bound to C-1 of the dihydroxyacetone phosphate (DHAP) moiety rather than by the more common cleavage at the acyl to oxygen bond. In the present study, the stereochemistry of this reaction was defined further; using deuterated substrates and fast atom bombardment-mass spectrometry, it was shown that the fatty acid exchange involves the stereospecific labilization of the pro-R hydrogen at C-1 of the DHAP moiety of acyl DHAP. The mechanism of ether bond formation, in which acyl DHAP is converted to O-alkyl DHAP, also proceeds via labilization of the pro-R hydrogen and cleavage of the fatty acid at the C-1 to oxygen bond. In addition, other workers have provided evidence that the enzyme responsible for the exchange reaction is O-alkyl DHAP synthetase. Therefore, the present results support the hypothesis that the acyl exchange is the reverse reaction of the first step O-alkyl DHAP synthesis; in both of these reactions the pro-R hydrogen of C-1 of the DHAP moiety of acyl DHAP and the fatty acid moiety are labilized with cleavage of the fatty acid at the DHAP C-1 to oxygen bond.

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