Stereoselective biosynthesis of chloroarylpropane diols by the basidiomycete Bjerkandera adusta

Chemosphere. 2003 Jul;52(2):503-12. doi: 10.1016/S0045-6535(03)00203-0.

Abstract

Previously we have shown that 1-arylpropane-1,2-diols are catabolic products of L-phenylalanine during idiophasic metabolism of B. adusta that are stereoselectively biosynthesized from a C(7)-unit (ring+benzylic carbon) and a C(2)-unit as predominantly erythro 1R, 2S enantiomers.In order to probe the mechanism of 1-arylpropane-1,2-diol formation, the products of the incubation of isotopically labelled aromatic aldehydes as substrates with Bjerkandera adusta (DAOM 215869) have been characterized. The aromatic aldehydes were benzaldehyde (ring D(5)) and 4-methoxy- and 4-hydroxybenzaldehydes (ring 13C(6)). These aldehydes were all stereoselectively incorporated into the corresponding 1-arylpropane-1,2-diols, including the chloro analogues, as well as into the corresponding alpha-ketols (phenyl acetyl carbinols (PAC's) and 2-hydroxy propiophenones (2-HPP's)) the presumed precursors of the diols. Benzoic acid (ring D(5)) was likewise incorporated into the diols, chlorodiols and alpha-ketols. These results lead us to conclude that the aromatic aldehydes benzaldehyde, 4-hydroxybenzaldehyde and 4-methoxybenzaldehyde are likely C(7)-unit precursors in the carboligation reaction(s) that leads to 1-arylpropane-1,2-diol biosynthesis. The metabolic role of the diols remains to be elucidated but they may be important intermediates in CAM (chlorinated anisyl metabolite) aldehyde-alcohol cycling and also act as substrates for the chlorination/hydroxylation enzymes yet to be identified in white rot fungi.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetylation
  • Alcohols / chemistry
  • Alcohols / metabolism*
  • Basidiomycota / metabolism*
  • Benzaldehydes / chemistry
  • Benzaldehydes / metabolism
  • Carbon Isotopes
  • Deuterium
  • Hydrocarbons, Aromatic / chemistry
  • Hydrocarbons, Aromatic / metabolism*
  • Hydrocarbons, Chlorinated / metabolism*
  • Keto Acids / chemistry
  • Keto Acids / metabolism
  • Propane / analogs & derivatives
  • Propane / chemistry
  • Propane / metabolism*
  • Spectrometry, Mass, Electrospray Ionization
  • Stereoisomerism

Substances

  • Alcohols
  • Benzaldehydes
  • Carbon Isotopes
  • Hydrocarbons, Aromatic
  • Hydrocarbons, Chlorinated
  • Keto Acids
  • Deuterium
  • Propane