The reactions of palladium(II), thallium(III) and lead(IV) trifluoroacetates with 3beta-acetoxyandrost-5-en-17-one: crystal structure of the first trifluoroacetate bridged 5,6,7-pi-allyl steroid palladium dimer.
A number of metal trifluoroacetates were reacted with the olefin 3beta-acetoxyandrost-5-en-17-one (6). Palladium(II) trifluoroacetate afforded bis[micro-trifluoroacetato(alpha-5,7-eta-3beta-acetoxyandrostenyl-17-one)palladium(II)] (20), a new ring B pi-allyl steroid-palladium complex, in quantitative yield. Thallium(III) trifluoroacetate gave 3beta-acetoxy-5alpha-hydroxy-6beta-trifluoroacetoxyandrostan-17-one (16), 3beta-acetoxy-6beta-trifluoroacetoxyandrost-4-en-17-one (9), 3beta-acetoxy-4beta-trifluoroacetoxyandrost-5-en-17-one (10), and 3beta-acetoxy-5alpha,6beta-dihydroxyandrostan-17-one (17). Lead(IV) trifluoroacetate yielded 9, 10 and 16. 3beta-Acetoxy-5alpha,6beta-bis(trifluoroacetoxy)androstan-17-one (15), a new compound, was also formed in this reaction. During the course of the lead(IV) studies the dichlorosteroid 21 and the rearranged allylic oxidation product 24 were formed. Their formation was attributed to the generation of lead(IV) chloride in the reaction. Silver(I) and copper(II) trifluoroacetates proved to be unreactive towards 6.
Ruddock
Peter L
PL
Chemistry Department, University of the West Indies, Mona, Kingston 7, Jamaica.
Williams
David J
DJ
Reese
Paul B
PB
D003461:Crystallography; D003687:Dehydroepiandrosterone / Q000031:analogs & derivatives* / Q000737:chemistry*; D019281:Dimerization; D007854:Lead / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013793:Thallium / Q000737:chemistry*; D014269:Trifluoroacetic Acid / Q000737:chemistry*
C495118:3beta-acetoxyandrost-5-en-17-one; D007854:Lead; D003687:Dehydroepiandrosterone; D010165:Palladium; D013793:Thallium; D014269:Trifluoroacetic Acid