Photo-induced molecular transformations. Part 87. Regiospecific photo-Beckmann rearrangement of steroidal α,β-unsaturated ketone oximes: synthesis of some steroidal enamino lactams

Steroidal lactams: a review

“…53 Acetylation of testosterone with acetic anhydride in pyridine led to the corresponding acetate which was condensed with hydroxylamine to provide the Z-and Eoximes 45. In a second step, a Beckman rearrangement of the mixture of 45 with SOCl2 in dioxane was realized and as predicted by previously described results, 54 a single lactam 46 was obtained in a moderate yield (63%) most likely due to Z/E isomerization before alkyl migration. Next, the acetyl moiety was deprotected under basic conditions with excellent yield (92%) and in a final step, the hydroxyl group at C-17 of the steroidal skeleton was esterified by POPAM 47 in the presence of DMAP and DCC in CH2Cl2 to provide, with a quantitative yield, the desired conjugate ENGA-L06E 48.…”

Photoinduced molecular transformations. Part 134. Photoinduced stereospecific addition of methanol to 5β-cholest-1-en-3-one oxime and photoinduced deconjugation of its 1-methyl derivative involving stereospecific proton transfer

“…The extract was worked up in the usual way. Evaporation of the solvent gave deuterio enone 11 (E)-2,4,4-Trideuterio-SP-cholest-1-en-3-one Oxime 18.-2,4,4-Trideuterio enone 11 (300 mg), hydroxylamine hydrochloride (380 mg), sodium acetate trihydrate (380 mg) and ethanol (24 cm3) were stirred together for 3 h at room temperature. Evaporation of the solvent gave a residue, which was extracted with diethyl ether.…”