Synthesis of some D-homo-18-norestrone derivatives
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Some reactions of the D-homo-18-nor steroid diketones (III) and (IV) were investigated. For the diketone (IV) ethynylation proceeds selectively with formation of the 17aα-alcohol (V), the structure of which was proved. By hydrogenation and Kizhner reduction of the ketol (V) 17aβ -vinyl-D-homo-18-norestra-1,3,5,9-tetraene-3,17aα-diol (XV) was obtained.
On ketalization of the diketones (II) and (IV) the same 17a-monoketal (XVII) was formed with inversion at C14 and migration of the double bond. By Kizhner reduction and subsequent hydrolysis (XVII) was converted into 3-hydroxy-D-homo-18-nor-14β -estra-1,3,5,8(9)-tetraen-17a-one (XXII). By the same route, but with hydrogenation of the intermediate ketal (XXI), 3-hydroxy-D-homo-19-nor-9β,14β -estra-1,3,5-trien-17a-one (XXIV) was obtained.
KeywordsHydrogenation Hydrolysis Migration Steroid Double Bond
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