title: The conversion of a phenol to an aniline occurs in the biochemical formation of the 1-(4-aminophenyl)-1-deoxy-D-ribitol moiety in methanopterin.
abstract: Recent work has demonstrated that 4-hydroxybenzoic acid is the in vivo precursor to the 1-(4-aminophenyl)-1-deoxy-D-ribitol (APDR) moiety present in the C(1) carrier coenzyme methanopterin present in the methanogenic archaea. For this transformation to occur, the hydroxyl group of the 4-hydroxybenzoic acid must be replaced with an amino group at some point in the biosynthetic pathway. Using stable isotopically labeled precursors and liquid chromatography with electrospray-ionization mass spectroscopy, the first step of this transformation in Methanocaldococcus jannaschii occurs by the reaction of 4-hydroxybenzoic acid with phosphoribosyl pyrophosphate (PRPP) to form 4-(β-d-ribofuranosyl)hydroxybenzene 5'-phosphate (β-RAH-P). The β-RAH-P then condenses with l-aspartate in the presence of ATP to form 4-(β-d-ribofuranosyl)-N-succinylaminobenzene 5'-phosphate (β-RFSA-P). Elimination of fumarate from β-RFSA-P produces 4-(β-D-ribofuranosyl)aminobenzene 5'-phosphate (β-RFA-P), the known precursor to the APDR moiety of methanopterin [White, R. H. (1996) Biochemistry 35, 3447-3456]. This work represents the first biochemical example of the conversion of a phenol to an aniline.
authors.affiliation: Department of Biochemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061-0308, USA. rhwhite@vt.edu
authors.forename: Robert H
authors.initials: RH
authors.lastname: White
mesh_terms: D010129:4-Aminobenzoic Acid / Q000138:chemical synthesis; D000814:Aniline Compounds / Q000138:chemical synthesis* / Q000378:metabolism; D019843:Archaeal Proteins / Q000138:chemical synthesis; D003067:Coenzymes / Q000138:chemical synthesis / Q000378:metabolism; D004722:Endoribonucleases / Q000138:chemical synthesis; D004792:Enzyme Precursors / Q000138:chemical synthesis; D017017:Methanococcus / Q000201:enzymology* / Q000235:genetics / Q000254:growth & development; D007652:Oxo-Acid-Lyases / Q000138:chemical synthesis; D019800:Phenol / Q000138:chemical synthesis* / Q000378:metabolism; D011622:Pterins / Q000138:chemical synthesis* / Q000378:metabolism; D012255:Ribitol / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000378:metabolism
chemical_list: D000814:Aniline Compounds; D019843:Archaeal Proteins; D003067:Coenzymes; D004792:Enzyme Precursors; D011622:Pterins; D019800:Phenol; D012255:Ribitol; C036686:methanopterin; D004722:Endoribonucleases; C109175:splicing endonuclease, Methanococcus; D007652:Oxo-Acid-Lyases; C075960:chorismate pyruvate lyase; C023650:aniline; D010129:4-Aminobenzoic Acid