Hydroxylation of α, β-Unsaturated Nitriles and Esters in Steroid Systems

Robert W. Freerksen, Michael L. Raggio, Carrie A. Thoms, David S. Watt

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The hydroxylation of α, β-unsaturated nitriles or α, β-unsaturated esters in various steroid systems using stoichiometric amounts of osmium tetroxide furnished -hydroxy ketones/aldehydes and α, β-dihydroxy esters in moderate yield. The absence of a C-21 acetoxy group in 17(20)-pregnene-20-carbonitriles or 5, 17(20)-pregnadiene-20-carbonitriles precluded using potassium permanganate to introduce the 17α-hydroxy 20-ketone synthon. However, the stoichiometric osmium tetroxide oxidation of various 17(20)-pregnene-20-carbonitriles furnished the 17α-hydroxy 20-ketones in moderate yield. α, β-Unsaturated nitriles derived from 3-ketones and 20-ketones were also hydroxylated to give α-hydroxy ketones and aldehydes in moderate yield. No regioselectivity for the Δ17, 20-double bond in 5, 17(20)-pregnadiene-20-carbonitriles was observed using osmium tetroxide. A catalytic osmium tetroxide-potassium chlorate oxidation of 17(20)-pregnene-20-carbonitriles required zinc nitrate to sequester cyanide ion liberated in the course of the hydroxylation. A brief investigation of osmium tetroxide oxidation of 5, 17(20)-pregnadienes bearing withdrawing groups at C-20 other than the nitrile disclosed an interesting hydroxylation of a 17(20)-unsaturated ester in the presence of a nonconjugated Δ5-double bond.

Original languageEnglish
Pages (from-to)702-710
Number of pages9
JournalJournal of Organic Chemistry
Volume44
Issue number5
DOIs
StatePublished - 1979

ASJC Scopus subject areas

  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Hydroxylation of α, β-Unsaturated Nitriles and Esters in Steroid Systems'. Together they form a unique fingerprint.

Cite this