(+)-9-氨基-4-去甲氧基-9-去氧柔红霉素酮的合成

Synthesis of (+)-9-Amino-4-demethoxy-9-deoxydaunomycinone

1,4-萘醌经氢化还原、甲基化、还原、环氧化、还原和氧化反应制得5,8-二甲氧基-2-萘满酮(8),经Strecker反应、甲酯化、拆分、酯缩合、还原、乙酰化反应得到(R)-(-)-2-乙酰基-2-乙酰胺基-5,8-二甲氧基-1,2,3,4-四氢萘(13)。13与邻苯二甲酸酐经傅-克酰化、缩酮化、光化反应和水解反应得到抗肿瘤药氨柔比星中间体(+)-9-氨基-4-去甲氧基-9-去氧柔红霉素酮。

（＋）-9-Amino-4-demethoxy-9-deoxydaunomycinone, a key intermediate of antitumor agent amrubicin, was synthesized from 1,4-naphthoquinone by reduction, methylation, reduction, epoxy reaction, reduction and oxidation to give 5,8-dimethoxy-2-tetralone, which was subjected to Strecker＇s reaction, esterification, resolution, ester condensation, reduction and acylation to afford （R） - （-） -2-acetyl-2-acetamido-5,8-dimethoxy-1,2,3,4- tetrahydronaphthalene, followed by Friedel-Crafts reaction with phthalic anhydride, protection with ethylene glycol, photochemical reaction and then hydrolysis.