Studies on Baeyer-Villiger oxidation of steroids: DHEA and pregnenolone D-lactonization pathways in Penicillium camemberti AM83.
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.
Kołek
Teresa
T
Department of Chemistry, Wrocław University of Environmental and Life Sciences, Norwida 25, 50-375 Wrocław, Poland.
Szpineter
Anna
A
Swizdor
Alina
A
D000735:Androstenedione / Q000378:metabolism; D000738:Androsterone / Q000378:metabolism; D003687:Dehydroepiandrosterone / Q000378:metabolism*; D007783:Lactones / Q000378:metabolism*; D010084:Oxidation-Reduction; D010407:Penicillium / Q000145:classification / Q000378:metabolism*; D011284:Pregnenolone / Q000378:metabolism*; D011374:Progesterone / Q000378:metabolism
D007783:Lactones; D000735:Androstenedione; D003687:Dehydroepiandrosterone; D011374:Progesterone; D011284:Pregnenolone; D000738:Androsterone