New Synthesis of 16β-Hydroxydehydroepiandrosterone and Related Ketols, with Special Reference to Preparation of Haptens

Abstract

A new method for the preparation of 16β-hydroxy-17-keto steroids has been developed. 16β-Hydroxylated dehydroepiandrosterone, epiandrosterone, androsterone and estrone were prepared from the corresponding 3, 16-diacetate through the 17-ethylenehemithioketal. 16β-Hydroxydehydroepiandrosterone 3-hemisuccinate for the use of immunoassay as a hapten was prepared from the 3β, 16β-dihydroxy-17-ketone ethylenehemithioketal by the sequential reactions : tert-butyldimethylsilylation of the hydroxyl functions, selective desilylation followed by hemisuccinylation at C-3, and removal of protecting groups at C-16 and C-17. The synthesis of the related 16, 17-ketol derivatives has also been described.