A Novel Route to 9α-Halo-11β-acyloxycorticosteroids

Design of ligands for the glucocorticoid and progestin receptors

“…However, the synthesis of some 9 a , 11Bdichloro analogues like dichlorisone [18] or RU 24476 (No. 6, Table 2) [ 191 showed that substitution of the hydroxyl by a chlorine leads to high affinity for both the GR and the PR.…”

Studies of the synthesis of 5-hydroxy 6-keto steroids and related 6-keto steroids

“…ref. 26). The structural assignments for 26 and 27 were based on comparison of their ' H nmr spectra with the spectrum of 5-bromo-5a-cholestane-3~,6~-diol 3-acetate 28, prepared by bromination of cholesteryl acetate (1) in aqueous medium (27).…”

A Novel Reduction with Alkylmercaptans and a New Route to 2-Keto Steroids

“…For example, 2 abromo-5a-cholestan-3-one reacts with potassium acetate in boiling acetic acid to give a 1:1 complex of 2 a-and fia-acetoxy-S-ketones.1 At 200°, these same reactants give a A5-4-keto steroid.2 A different source of acetate ion, tetramethylammonium acetate, causes 2abromo-5a-cholestan-3-one to form 3/3-acetoxy-5a-cholestan-2-one. 3 In the acid-catalyzed methanolysis of 2-acetoxytestosterone, the 2/3-epimer yields 17/3-hydroxy-5a-androstane-3,6-dione,4 whereas the 2a-epimer yields 2-methoxy-4-methyl-1,3,5(10)-estratrien-17/3-ol.5…”