The identification of (3R,4S)-5-fluoro-5-deoxy-D-ribulose-1-phosphate as an intermediate in fluorometabolite biosynthesis in Streptomyces cattleya.
(3R,4S)-5-Fluoro-5-deoxy-D-ribulose-1-phosphate (5-FDRulP) has been identified as the third fluorinated intermediate on the biosynthetic pathway to fluoroacetate and 4-fluorothreonine in Streptomyces cattleya. 5-FDRulP is generated after formation of 5'-fluoro-5'-deoxyadenosine (5'-FDA) and then phosphorolysis of 5'-FDA to 5-fluoro-5-deoxy-D-ribose-1-phosphate (5-FDRP) by the action of a purine nucleoside phosphorylase. An isomerase mediates the conversion of 5-FDRP to 5-FDRulP. The identity of the (3R,4S) diastereoisomer of 5-FDRulP was established by comparative (19)F{(1)H} NMR studies whereby 5-FDRulP that accumulated in a cell free extract of S. cattleya, was treated with a phytase to generate the non-phosphorylated sugar, 5-fluoro-5-deoxy-D-ribulose (5-FDRul). This S. cattleya product was compared to the product of an in-vitro biotransformation where separately 5-fluoro-5-deoxy-D-ribose and 5-fluoro-5-deoxy-D-xylose were converted to 5-fluoro-5-deoxy-D-ribulose and 5-fluoro-5-deoxy-D-xylulose respectively by the action of glucose isomerase. It was demonstrated that 5-fluoro-5-deoxy-D-ribose gave the identical diastereoisomer to that observed from 5-FDRulP.
Onega
Mayca
M
School of Chemistry and Centre for Biomolecular Science, University of St Andrews, North Haugh, St Andrews KY16 9ST, UK.
McGlinchey
Ryan P
RP
Deng
Hai
H
Hamilton
John T G
JT
O'Hagan
David
D
D019747:Aldose-Ketose Isomerases / Q000737:chemistry; D001426:Bacterial Proteins / Q000737:chemistry; D053898:Biosynthetic Pathways; D002384:Catalysis; D002474:Cell-Free System; D005463:Fluoroacetates / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D010088:Oxidoreductases / Q000737:chemistry; D006005:Phosphorylases / Q000378:metabolism; D020033:Protein Isoforms; D012274:Ribulosephosphates / Q000737:chemistry*; D013302:Streptomyces / Q000737:chemistry* / Q000378:metabolism
D001426:Bacterial Proteins; D005463:Fluoroacetates; D020033:Protein Isoforms; D012274:Ribulosephosphates; C047513:1-fluoro-1-deoxyribulose-5-phosphate; D010088:Oxidoreductases; C495766:fluorinase; D006005:Phosphorylases; D019747:Aldose-Ketose Isomerases; C023298:xylose isomerase