马烯雌酮及其衍生物的高效合成

Practical Syntheses of Equilin and Its Derivatives

马烯雌酮及其衍生物是结合雌激素药物的重要组成成分,主要从孕马尿中提取获得.由于存在不稳定的非共轭双键,化学合成非常困难.以商品化的19-羟基-4-烯-3,17-二酮雄甾为原料,retro-aldol芳构化反应为关键步骤,分别以32%,37%和25%的收率合成了马烯雌酮(7)、17β-二氢马烯雌酮(8)和17α-二氢马烯雌酮(9).

Equilin and its derivatives are important active ingredients of conjugated estrogens, extracted from pregnant horse urine. However, they are still challenge synthetic targets due to the presence of an unstable non-conjugated double bond.Equilin（7）, 17β-dihydroequilin（8） and 17α-dihydroequilin（9） were efficiently synthesized from commercially available 19-hydroxyandrost-4-ene-3,17-dione via retro-aldol aromatization with the overall yields of 32%, 37% and 25%, respectively.