Studies on Baeyer-Villiger oxidation of steroids: DHEA and pregnenolone D-lactonization pathways in Penicillium camemberti AM83

Steroids. 2009 Oct;74(10-11):859-62. doi: 10.1016/j.steroids.2009.05.007. Epub 2009 May 28.

Abstract

Penicillium camemberti AM83 strain is able to carry out effective Baeyer-Villiger type oxidation of DHEA, pregnenolone, androstenedione and progesterone to testololactone. Pregnenolone and DHEA underwent oxidation to testololactone via two routes: through 4-en-3-ketones (progesterone and/or androstenedione respectively) or through 3beta-hydroxy-17a-oxa-d-homo-androst-5-en-17-one. Analysis of transformation progress of studied substrates as function of time indicates that the 17beta-side chain cleavage and oxidation of 17-ketones to d-lactones are catalyzed by two different, substrate-induced, BVMOs. In the presence of a C-21 substrate (pregnenolone or progesterone) induction of the enzyme catalyzing cleavage at 17beta-acetyl chain was observed, whereas DHEA and androstenedione induced activity of the BVMO responsible for the ring-D oxidation; 5-en-3beta-alcohol was a more effective inducer that the respective 4-en-3-ketone.

MeSH terms

  • Androstenedione / metabolism
  • Androsterone / metabolism
  • Dehydroepiandrosterone / metabolism*
  • Lactones / metabolism*
  • Oxidation-Reduction
  • Penicillium / classification
  • Penicillium / metabolism*
  • Pregnenolone / metabolism*
  • Progesterone / metabolism

Substances

  • Lactones
  • Androstenedione
  • Dehydroepiandrosterone
  • Progesterone
  • Pregnenolone
  • Androsterone