26 人尿中のProstaglandins代謝物の合成

概要

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The main urinary metabolites of prostaglandins F_<2α> (1) and E_2 (2) were recently isolated and identified as 5α,7α-dihydroxy-11-ketotetranorprosta-1,16-dioic acid (3) and/or its δ-lactone (4), and 7α-hydroxy-5,11-diketotetranorprosta-1,16-dioic acid (5) respectively. Interest on biological activities of prostaglandin metabolites promoted us their synthesis. The γ-lactone (6), which was already stereospecifically synthesized, was chosen as a starting intermediate and transformed to six menbered lactone (7) by five steps: diisobutylaluminium-hydride reduction, Wittig reaction in order to introduce one more carbon atom, acid-catalized hydrolysis, and silver oxide oxidation followed by acetylation. The δ-lactone (7) thus obtained was converted to the α,β-unsaturated keto-lactone (20) by three steps: boron tribromide de-methylation, chromium trioxide pyridine complex oxidation, and condensation with dimethyl 2-keto-6-carbomethoxy-hexylphosphonate (19). Catalytic hydrogenation of the enone (20) afforded the keto-lactone (21) which was hydrolized to give the prostaglandin F_<2α> metabolite (4). The identity of the metabolite (4) was confirmed by comparison of mass spectrum of the methoxime derived from keto-lactone(21).
天然有機化合物討論会の論文
1972-10-01