4-Androstenedione can be synthesized in one of two ways. The primary pathway involves conversion of 17-hydroxypregnenolone to dehydroepiandrosterone by way of 17,20-lyase, with subsequent conversion of dehydroepiandrosterone to 4-Androstenedione via the enzyme 3-β-hydroxysteroid dehydrogenase. The secondary pathway involves conversion of 17-hydroxyprogesterone, most often a precursor to cortisol, to 4-androstenediones directly by way of 17,20-lyase. Thus, 17,20-lyase is required for the synthesis of 4-androstenediones, whether immediately or one step removed.
The production of adrenal 4-Androstenedione is governed by ACTH, whereas production of gonadal 4-Androstenedione is under control by gonadotropins. In premenopausal women, the adrenal glands and ovaries each produce about half of the total 4-androstenedione(about 3 mg/day). After menopause, 4-androstenedione production is about halved, due primarily to the reduction of the steroid secreted by the ovary. Nevertheless, 4-androstenedione is the principal steroid produced by the postmenopausal
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