Collect. Czech. Chem. Commun. 1997, 62, 1631-1641

The Synthesis of A-Homo-B-norandrostanes: The Effect of a Hydroxyl on the Course of Hydrogenation of the ∆9-Double Bond

Alexander Kasal, Barbora Slavíková, Ladislav Kohout and Miloš Buděšínský

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic


Acetolysis of 6β-mesyloxy-5-methyl-19-nor-5β-steroids (e.g. 10) was proved to yield 4a-homo-7,19-dinor compounds (e.g. 9) with a hydroxy group in the position 4aα. Hydrogenation of these compounds affords 9β,10β-dihydro derivatives (e.g. 12) predominantly, corresponding 9α,10α isomers (e.g. 13) are only formed in low yields. This sequence was used for the synthesis of analogues of androgen hormones 4aα-hydroxy-4aβ-methyl-4a-homo-7,19-dinor-5α,9β,10β- androstane-3,17-dione (27), 4aα,17β-dihydroxy-4aβ,17α-dimethyl-4a-homo-7,19-dinor-5α,9β,10β-androstan-3-one (28) and 4aα,17β-dihydroxy-4aβ-methyl-4a-homo-7,19-dinor-5α,9β,10β-androstan-3-one (29).

Keywords: NOE experiments; Hormone analogues; Steroid skeletal rearrangement; Ketone circular dichroism; Steroids.