Towards preparative scale steroid hydroxylation with cytochrome P450 monooxygenase CYP106A2

Chembiochem. 2010 Mar 22;11(5):713-21. doi: 10.1002/cbic.200900706.

Abstract

Cytochrome P450 monooxygenases are of outstanding interest for the synthesis of pharmaceuticals and fine chemicals, due to their ability to hydroxylate C--H bonds mainly in a stereo- and regioselective manner. CYP106A2 from Bacillus megaterium ATCC 13368, one of only a few known bacterial steroid hydroxylases, enables the oxidation of 3-keto-4-ene steroids mainly at position 15. We expressed this enzyme together with the electron-transfer partners bovine adrenodoxin and adrenodoxin reductase in Escherichia coli. Additionally an enzyme-coupled cofactor regeneration system was implemented by expressing alcohol dehydrogenase from Lactobacillus brevis. By studying the conversion of progesterone and testosterone, the bottlenecks of these P450-catalyzed hydroxylations were identified. Substrate transport into the cell and substrate solubility turned out to be crucial for the overall performance. Based on these investigations we developed a new concept for CYP106A2-catalyzed steroid hydroxylations by which the productivity of progesterone and testosterone conversion could be increased up to 18-fold to yield an absolute productivity up to 5.5 g L(-1) d(-1). Product extraction with absorber resins allowed the recovery of quantitative amounts of 15beta-OH-progesterone and 15beta-OH-testosterone and also the reuse of the biocatalyst.

MeSH terms

  • Adrenodoxin / genetics
  • Adrenodoxin / metabolism
  • Alcohol Dehydrogenase / metabolism
  • Animals
  • Bacterial Proteins / chemistry
  • Bacterial Proteins / metabolism*
  • Cattle
  • Cytochrome P-450 Enzyme System / chemistry
  • Cytochrome P-450 Enzyme System / metabolism*
  • Ferredoxin-NADP Reductase / genetics
  • Ferredoxin-NADP Reductase / metabolism
  • Hydroxylation
  • Oxidation-Reduction
  • Progesterone / biosynthesis*
  • Solubility
  • Stereoisomerism
  • Testosterone / biosynthesis*

Substances

  • Bacterial Proteins
  • Adrenodoxin
  • Testosterone
  • Progesterone
  • Cytochrome P-450 Enzyme System
  • Alcohol Dehydrogenase
  • 15beta-hydroxylase CYP106A2, Bacillus megaterium
  • Ferredoxin-NADP Reductase