15-deoxy and 11,15-bisdeoxy derivatives of prostaglandins

摘要

1429081 Prostaglandins; organometallic compounds G D SEARLE & CO 1 Feb 1973 [3 Feb 1972] 4998/73 Headings C2C and C2J Novel prostaglandins of the Formula I: wherein X is CH 2 or C(ORSP2/SP)H, wherein RSP2/SP is H or C 1-7 alkanoyl, R is H or C 1-7 alkyl, Z is vinylene or ethynylene, m is 6 or 7, n is 3, 4 or 5, and the wavy lines represent the alternative alpha or beta configuration or the epimeric mixture; provided that when X is CH 2 , then Z is -C#C-, are prepared by reacting cyclopentene derivatives of the Formula II: wherein Y is CH 2 or C(ORSP3/SP)H, wherein RSP3/SP is H, C 1-7 alkenoyl or 2-tetrahydropyranyl, and RSP3/SP is H, C 1-7 alkyl or 2-tetrahydropyranyl with compounds of the formulµ and, if necessary, hydrolysing the resulting compounds of Formula I in which RSP2/SP and/or R are 2-tetrahydropyranyl. Optically active methyl 3-hydroxy-5-oxocyclopent-1-eneheptanoate is obtained by hydrolysing the corresponding methyl 3-hydroxy-5-[(1-carboxy - 3 - methybutyl)oxyimino]cyclopent- 1- eneheptanoate, resulting from the chromatography of the mixture obtained by reacting 2(S)-aminooxy-4-methylvaleric acid and racemic methyl 3-hydroxy-5-oxocyclopent-1-eneheptenoate, which is prepared by esterifying the corresponding acid. The trans-1-alkenyl copper compounds of the formula CH 3 (CH 2 ) n CH=CH-Cu are prepared by the addition of cuprous iodide to a solution of the corresponding trans-1-alkenyl magnesium chlorides, obtained by contacting magnesium, activated with mercuric chloride, with trans-1- alkenyl mercuric chloride, which is obtained by contacting the corresponding 1-alkynes with catechol borane and treating the product with mercuric chloride. The cis-1-alkenyl copper compounds are obtained by treating the appropriate cis-1- alkenyl bromides successively with lithium and cuprous iodide. The trialkynyl aluminium compounds are prepared by treating the appropriate 1-alkyne with butyl lithium and then with aluminium chloride.