Totally synthetic steroid hormones—VI

A + D → Ad → Abcd

“…In a similar manner, 1 (R = OH, or R = H) gave rise to the corresponding 2 (R = OH, or R = H) [4]. Still further experimentation led to the «-methyl homolog of 2 (R = OMe) [9]. Mannich condensation of 2 with formalin and diethylamine in the presence of acetic acid and cuprous chloride gave very good yields of 3 which was hydrated to the ketone 4 using sulfuric acid and mercuric sulfate.…”

Pentacyclic steroids. 3. Synthesis of 4,6.alpha.-ethanoestradiol, 4,6.alpha.-ethanoestrone, and 17.alpha.-ethynyl-4,6.alpha.-ethanoestradiol

“…The organic layers were washed with water, combined, dried over MgS04, and filtered. Removal of the solvent provided a mixture of 4 and 15. This was refluxed for 2 h with a solution of KOH (0.14 g) in 4.5 mL of CH3OH and 0.5 mL of water.…”

“…Clemmensen reduction of 14 yielded a mixture of 15 and 4, which, upon base hydrolysis and subsequent acidification, gave 4,6a-ethanoestradiol (4). Methylation of 4 formed 16, whereas oxidation with Cr03 yielded 4,6a-ethanoestrone (5).…”

Stereoselective biomimetic total synthesis of 6.alpha.-methyl-19-norsteroids

“…Tnese values compare well with reported data. 5 The stereochemistry was proven unambiguously by the conversion of 8a into compounds with known structure (vide infra). The NMR spectrum of the mother liquor showed an additional doublet centered at 1.28 attributed to the 60-isomer 8b (cf.…”