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

Biochemistry. 2011 Jul 12;50(27):6041-52. doi: 10.1021/bi200362w. Epub 2011 Jun 15.


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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • 4-Aminobenzoic Acid / chemical synthesis
  • Aniline Compounds / chemical synthesis*
  • Aniline Compounds / metabolism
  • Archaeal Proteins / chemical synthesis
  • Coenzymes / chemical synthesis
  • Coenzymes / metabolism
  • Endoribonucleases / chemical synthesis
  • Enzyme Precursors / chemical synthesis
  • Methanococcus / enzymology*
  • Methanococcus / genetics
  • Methanococcus / growth & development
  • Oxo-Acid-Lyases / chemical synthesis
  • Phenol / chemical synthesis*
  • Phenol / metabolism
  • Pterins / chemical synthesis*
  • Pterins / metabolism
  • Ribitol / analogs & derivatives*
  • Ribitol / chemical synthesis*
  • Ribitol / metabolism


  • Aniline Compounds
  • Archaeal Proteins
  • Coenzymes
  • Enzyme Precursors
  • Pterins
  • Phenol
  • Ribitol
  • methanopterin
  • Endoribonucleases
  • splicing endonuclease, Methanococcus
  • Oxo-Acid-Lyases
  • chorismate pyruvate lyase
  • aniline
  • 4-Aminobenzoic Acid