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本文报告dl-PGF_(2α)的定向合成。从环戊二烯出发,经四步反应先合成得环戊烯二醇(Ⅸ),然后用40％过醋酸立体选择性地引入一个环氧而得双羟环氧物(Ⅹ),此物用辛炔-1-叔丁醚-3的二乙基铝(Ⅺ_c)开裂氧环,即可一步引入前列腺素分子中所需的一个C_(12)-八碳醇侧链,得开环物(Ⅻ),侧链在五元环上的位置通过与Corey合成路线中的中问体(ⅩⅩⅤ)相联系得到证明。 开环物(Ⅻ)用MnO_2氧化时,主要得内酯(ⅩⅢ),然后经(i-Bu)_2AlH还原、Wittig反应引入羧酸侧链、再用三氟乙酸水解15-叔丁醚基,即得13-去氢PGF_(2α),后者用Na-NH_3-t-BuOH进行炔键的选择性还原,用硅胶柱进行分离,可得dl-PGF_(2α)和dl-15-epi-PGF_(2α)。
This article reports the directional synthesis of dl-PGF_ (2α). Starting from cyclopentadiene, cyclopentenediol (IX) is first synthesized in four steps and then stereoselectively introduced into an epoxy with 40% peracetic acid to give the bishydroxyepoxide (X), which Oxygen is cleaved by diethylaluminum (XI-c) of octyne-1-tert-butyl ether-3 to introduce one C 12-octadecanol side chain in the prostaglandin molecule in one step, (Ⅻ), the position of the side chain on the five-membered ring is evidenced by the interrogation (XXV) in Corey’s synthetic route. When the ring-opening product (Ⅻ) is oxidized with MnO 2, the main lactone (XIII) is then reduced with (i-Bu) _2AlH, the Wittig reaction introduces the carboxylic acid side chain, and the trifluoroacetic acid is used to hydrolyze the 15- 13-dehydro-PGF2α, the latter by Na-NH3-t-BuOH acetylenic bond selective reduction using silica gel column separation, available dl-PGF2alpha and dl-15-epi-PGF_ 2α).