合成路线:Treatment of the optically pure lactone (I) with lithium dimethyl methylphosphonate in tetrahydrofuran gives hemiacetal (II),which is oxidized to the diketone (III) using Jones' reagent in acetone.Then in the key step,compound (III) cyclizes to enone (IV) using potassium carbonate and 18-crown-6 in warm toluene.Lithium dimethyl cuprate addition to enone (IV) in ether gives ketone (V),which is converted to acid (VI) (a 1:1 mixture of E and Z olefins at C-5) using (4-carboxybutyl)triphenylphosphorane in dimethyl sulfoxide.Cleavage of the alcohol-protecting groups in (VI) with an acetic acid-water-tetrahydrofuran mixture followed by chromatography to remove the 5-E isomer affords 9-methylcarbacyclin (VII).Finally,treatment of (VII) with calcium oxide in tetrahydrofuran gives U-61431F (ciprostene calcium).
参考文献标题:Ciprostene Calcium
文献作者:Aistoff,P.A.
参考来源:Drugs Fut 1985,10(11),900
合成路线:Treatment of the optically pure lactone (I) with lithium dimethyl methylphosphonate in tetrahydrofuran gives hemiacetal (II),which is oxidized to the diketone (III) using Jones' reagent in acetone.Then in the key step,compound (III) cyclizes to enone (IV) using potassium carbonate and 18-crown-6 in warm toluene.Lithium dimethyl cuprate addition to enone (IV) in ether gives ketone (V),which is converted to acid (VI) (a 1:1 mixture of E and Z olefins at C-5) using (4-carboxybutyl)triphenylphosphorane in dimethyl sulfoxide.Cleavage of the alcohol-protecting groups in (VI) with an acetic acid-water-tetrahydrofuran mixture followed by chromatography to remove the 5-E isomer affords 9-methylcarbacyclin (VII).Finally,treatment of (VII) with calcium oxide in tetrahydrofuran gives U-61431F (ciprostene calcium).
参考文献标题:Synthesis of 9-subtituted cabacyclin analogues
文献作者:Aristoff,P.A.; Harrison,A.W.; Johnson,P.D.
参考来源:J Org Chem 1983,485341
合成路线:Treatment of the optically pure lactone (I) with lithium dimethyl methylphosphonate in tetrahydrofuran gives hemiacetal (II),which is oxidized to the diketone (III) using Jones' reagent in acetone.Then in the key step,compound (III) cyclizes to enone (IV) using potassium carbonate and 18-crown-6 in warm toluene.Lithium dimethyl cuprate addition to enone (IV) in ether gives ketone (V),which is converted to acid (VI) (a 1:1 mixture of E and Z olefins at C-5) using (4-carboxybutyl)triphenylphosphorane in dimethyl sulfoxide.Cleavage of the alcohol-protecting groups in (VI) with an acetic acid-water-tetrahydrofuran mixture followed by chromatography to remove the 5-E isomer affords 9-methylcarbacyclin (VII).Finally,treatment of (VII) with calcium oxide in tetrahydrofuran gives U-61431F (ciprostene calcium).
参考文献标题:Practical synthesis of 6a-carbaprostaglandin I2
文献作者:Aristoff,P.A.
参考来源:J Org Chem 1981,461954
产品链接: CAS No. 81703-55-1›› 产品链接: CAS No.81845-44-5››