63518-24-1Relevant academic research and scientific papers
Syntheses of (E)- and (Z)-volkendousin
Snider, Barry B.,Shi, Bo
, p. 14823 - 14828 (1999)
The first syntheses of the antitumor agents (E)-volkendousin (1) and acetonide 3 have been accomplished by efficient routes from readily available dehydroisoandrosterone (7) using allylic oxidation with SeO2 to introduce the 4β-hydroxy group and 16- ketone. This sequence should make these compounds readily available for further biological evaluation.
The scope and limitations of the reaction of Δ5-steroids with mercury(II) trifluoroacetate
Ruddock, Peter L.D.,Williams, David J.,Reese, Paul B.
, p. 650 - 664 (2007/10/03)
The effect of the C-3 substituent on the reaction of androst-5-enes with mercury(II) trifluoroacetate in dichloromethane (modified Treibs oxidation) was investigated. 3β-Acyloxyandrost-5-en-17-ones gave 3β-acyloxy-6β- hydroxyandrost-4-en-17-ones accompanied by 3β-acyloxy-6- chloromercuriandrost-5-en-17-ones. 3β-Acetoxy-6β-trifluoroacetoxyandrost- 4-en-17-one and 3β-acetoxy-4β-trifluoroacetoxyandrost-5-en-17-one were revealed to be intermediates in the reaction. The formation of the chloromercury steroids indicated participation in the reaction by the solvent. With 3α-acetoxyandrost-5-en-17-one as substrate, a complete reversal in the product distribution was observed. 3β-Haloandrost-5-en-17- ones gave mainly products that reflected S(N)1 substitution of the halide. 3β-Hydroxy- and 3β-trifluoroacetoxyandrost-5-en-17-ones were formed. 3β- Methoxyandrost-5-en-17-one afforded in nearly identical yields androst-4- ene-3,17-dione, 3β-methoxy-6β-hydroxyandrost-4-en-17-one, 3β-methoxy-6- chloromercuriandrost-5-en-17-one and 6β-hydroxyandrost-4-ene-3,17-dione while androst-5-en-17-one yielded 3β,6β-dihydroxyandrost-4-en-17-one, androst-5-ene-7,17-dione and androst-4-ene-3,17-dione. The effects of solvent and other mercury salts on the reaction were also studied. Treibs oxidation was successful in chloroform, carbon tetrachloride, and dibromomethane, but not in other solvents tested. 3β-Acetoxy-6-bromomercuriandrost-5-en-17-one was obtained in dibromomethane. Replacement of the reagent by mercury(II) trichloroacetate altered the intermediates formed but not the products. Mercury(II) tribromoacetate was unreactive, however.
Allylic Acetoxylation of Δ5-Steroids at C-4
Hanson, James R.,Reese, Paul B.,Wadsworth, Harry J.
, p. 2941 - 2944 (2007/10/02)
The allylic acetoxylation of Δ5-steroids at C-4 by reaction with bromine and silver acetate has been shown to depend upon the nature of the C-3 substituent. 2H Labelling studies have shown that the reaction, which proceeds via the 5α,6β-dibromide, involves the trans diaxial elimination of a 4β-proton to form a Δ4-6β-bromide which then undergoes an SN2' displacement by the incoming acetate assisted by the silver ion.
The Solvolysis of 4β-Hydroxy-3β-p-tolylsulphonyloxyandrost-5-enes
Hanson, James R.,Wadsworth, Harry J.
, p. 933 - 937 (2007/10/02)
The solvolysis of 3β-p-tolylsulphonyloxyandrost-5-enes in acetic acid containing sodium acetate, is retarded by the presence of a 4β-acetoxy- or hydroxy-group.The products of solvolysis include the A-nor-3-formyl-steroids except in the presence of a 7-ketone.
