Abstract
In order to clarify the stereochemistry of hydrogen loss from C-2 and C-4 during the microbial ⊿1- and ⊿4-dehydrogenation the titled compounds have been synthesized as the suitable substrates. The key intermediates leading to the desired compounds, ⊿2- and ⊿3-olefins (V, VI), were prepared from 5β-androstane-3α, 17β-diol 3-tosylate 17-acetate (IV). Epoxidation with per-acid followed by trans-diaxial opening of the resulting β-epoxides (VII, VIII) with lithium aluminum deuteride gave 2α- and 4α-deuterio-5β-androstane-3β, 17β-diols (X, XIV). On the other hand V and VI were transformed into the 2β- and 4β-deuterio-3β, 17β-diols (XII, XVI) by treatment with deuterated diborane and then with hydrogen peroxide. Upon oxidation with chromium trioxide-pyridine complex these labeled diols were led to the 2- and 4-deuterated 3, 17-diketones (XI, XIII, XV, XVII), respectively.
