Sih J C, Johnson R A, Nidy E G, Graber D R
Prostaglandins. 1978 Mar;15(3):409-21. doi: 10.1016/0090-6980(78)90124-7.
We wish to report here the syntheses of (5S, 6R)-5-hydroxy-, (5R, 6R)-5-hydroxy-, (5R, 6S)-5-hydroxy-, and (5S, 6S)-5-hydroxy-PGI1 and their methyl ester derivatives. Treatment of (5R, 6S)-epoxy- and (5S, 6R)-epoxy-PGF1alpha methyl esters with acid washed silica gel afforded (5R, 6R)-5-hydroxy- and (5S, 6S)-5-hydroxy-PGI1 methyl esters; correspondingly, silica promoted cyclization of (5S, 6S)-epoxy- and (5R, 6R)-epoxy-PGF1alpha methyl esters yielded (5S, 6R)-5-hydroxy- and (5R, 6S)-5-hydroxy-PGI1 methyl esters. Alternatively, the 5-hydroxyl group was introduced into the PGI1 skeleton via reaction of the 5-mercuric halides with sodium borohydride in the presence of oxygen. Stereochemical assignments were based on their mode of synthesis and 1H nmr shift differences.
我们在此报告(5S, 6R)-5-羟基、(5R, 6R)-5-羟基、(5R, 6S)-5-羟基和(5S, 6S)-5-羟基前列环素I1（PGI1）及其甲酯衍生物的合成。用酸洗硅胶处理(5R, 6S)-环氧和(5S, 6R)-环氧前列地尔F1α甲酯，得到(5R, 6R)-5-羟基和(5S, 6S)-5-羟基前列环素I1甲酯；相应地，硅胶促进(5S, 6S)-环氧和(5R, 6R)-环氧前列地尔F1α甲酯环化，生成(5S, 6R)-5-羟基和(5R, 6S)-5-羟基前列环素I1甲酯。另外，通过5-卤化汞与硼氢化钠在氧气存在下反应，将5-羟基引入前列环素I1骨架。立体化学归属基于它们的合成方式和1H核磁共振位移差异。
