Abstract:Application of [1,2-14 C]1-deoxy-D-xylulose, the committed precursor of terpenoids, thiamine and pyridoxol, to a variety of plant species resulted in the labelling of an unknown metabolite. The isolation and purification of this metabolite from Ipomoea purpurea plants fed with 1-deoxy-D-xylulose (DX), followed by NMR analysis, resulted in the identification of its structure as (3)-2C-methyl-D-erythrono-1,4-lactone (MDEL). MDEL has been previously isolated as a stress metabolite of certain plants. A hypothetica… Show more
“…The uniqueness of the epimerization reaction described herein assumes further significance when the close correspondence is noted between the Mo-catalyzed interconversion of 9 and 2 and the proposed metabolism of 1 via the non-mevalonate isoprenoid pathway. It has been suggested that 1 is converted in vivo to 2- C -(methyl)- d -erythritol 4P via tandem pinacol rearrangement/reduction during its metabolism. − The molybdate-catalyzed rearrangement described herein mimics this biological transformation. In the metabolic pathway, no evidence exists implicating the involvement of molybdenum in the pinacol rearrangement.…”
mentioning
confidence: 84%
“…In most eukaryotic organisms and archaebacteria, the mevalonate pathway is responsible for the biosynthesis of isoprenoid compounds wherein acetyl CoA serves as the metabolic precursor. Recent studies, however, suggest that 1-deoxy- d -xylulose 5-phosphate 1 serves as a precursor in the biosynthesis of isoprenoids in bacteria, green algae, and plants, as well as in the biosynthesis of vitamins B 6 and B 1 . − Interest in elucidating these new pathways has stimulated recent reports on the preparation of 1-deoxy- d -xylulose 2 and its 5-phosphate 1 . − Here we describe a chemical route to 2 (Scheme 1) involving a unique carbon skeleton rearrangement that mimics one of the putative metabolic reactions of these pathways. …”
1-Deoxy-D-xylulose has been prepared in seven steps and approximately 21% overall yield from 2,3-O-isopropylidene-D-erythrono-1,4-lactone. The key reaction involves transformation of a branched-chain aldotetrose to the 1-deoxy-2-ketopentose catalyzed by molybdic acid. Other branched-chain aldotetroses containing bulkier substituents at C2 also engage in the conversion, suggesting routes to protected 2-ketoses and alpha-ketoacids/esters. This synthetic route mimics reactions of the non-mevalonate isoprenoid pathway in plants and bacteria. [reaction: see text]
“…The uniqueness of the epimerization reaction described herein assumes further significance when the close correspondence is noted between the Mo-catalyzed interconversion of 9 and 2 and the proposed metabolism of 1 via the non-mevalonate isoprenoid pathway. It has been suggested that 1 is converted in vivo to 2- C -(methyl)- d -erythritol 4P via tandem pinacol rearrangement/reduction during its metabolism. − The molybdate-catalyzed rearrangement described herein mimics this biological transformation. In the metabolic pathway, no evidence exists implicating the involvement of molybdenum in the pinacol rearrangement.…”
mentioning
confidence: 84%
“…In most eukaryotic organisms and archaebacteria, the mevalonate pathway is responsible for the biosynthesis of isoprenoid compounds wherein acetyl CoA serves as the metabolic precursor. Recent studies, however, suggest that 1-deoxy- d -xylulose 5-phosphate 1 serves as a precursor in the biosynthesis of isoprenoids in bacteria, green algae, and plants, as well as in the biosynthesis of vitamins B 6 and B 1 . − Interest in elucidating these new pathways has stimulated recent reports on the preparation of 1-deoxy- d -xylulose 2 and its 5-phosphate 1 . − Here we describe a chemical route to 2 (Scheme 1) involving a unique carbon skeleton rearrangement that mimics one of the putative metabolic reactions of these pathways. …”
1-Deoxy-D-xylulose has been prepared in seven steps and approximately 21% overall yield from 2,3-O-isopropylidene-D-erythrono-1,4-lactone. The key reaction involves transformation of a branched-chain aldotetrose to the 1-deoxy-2-ketopentose catalyzed by molybdic acid. Other branched-chain aldotetroses containing bulkier substituents at C2 also engage in the conversion, suggesting routes to protected 2-ketoses and alpha-ketoacids/esters. This synthetic route mimics reactions of the non-mevalonate isoprenoid pathway in plants and bacteria. [reaction: see text]
“…The feeding of labelled deoxyxylulose to Ipomoea purpurea plants leads to formation of a metabolite, identified as 2-C-methyl--erythrono-1,4-lactone 20. 51 Similar transformation occurs in a variety of plant systems. This compound had previously been isolated as a stress metabolite in certain plants.…”
This review covers recently-published experimental information on the biosynthesis of terpenoids in the range C5-C25. In addition to sections on the mevalonate and mevalonate-independent (deoxyxylulose phosphate) pathways, the review considers in turn hemiterpenoids, polyprenyl diphosphate synthases, monoterpenoids, sesquiterpenoids, diterpenoids, and sesterterpenoids. The literature from January 1998 to December 2000 is reviewed, with 248 references cited.
“…45 However another product, (À)-2C-methyl-D-erythrono-1,4-lactone 54 has recently been shown to be derived from DX in plants. 46 The sequence of events probably involves 2C-methyl-D-erythritol-4-phosphate 55 as an intermediate, with the later steps involving oxidation at carbon-1 and lactonisation (Scheme 17).…”
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