合成路线:The reaction of 4-hydroxy-1-octyne (I),with chlorotrimethylsilane and imidazole in DMF gives 4-trimethylsilyloxy-1-octyne (II),which is converted into 1-iodo-4-trimethylsilyloxy-trans-1-octene (III) by reaction with bis(3-methyl-2-butyl)borane (A),trimethylamine oxide,NaOH and finally I2.The hydrolysis of (III) with acetic acid in THF affords 1-iodo-4-hydroxy-trans-1-octene (IV),which is oxidized with pyridinium chlorochromate in methylene chloride yielding 1-iodo-4-oxo-trans-1-octene (V).The Grignard reaction of (V) with vinylmagnesium bromide (B) in THF gives 4-hydroxy-4-vinyl-1-iodo-trans-1-octene (VI),which is protected with trimethylsilyl chloride as before yielding 4-trimethylsilyloxy-4-vinyl-1-iodo-trans-1-octene (VII).The reaction of (VII) with tert-butyllithium in ether and then with copper (1)-1-pentyne-tributylphosphine (C) in HMPT affords the copper salt (VIII),which is condensed with 2-(6-trimethylsilyloxycarbonyl-2-cis-hexenyl)-4-trimethylsilyloxycyclopent-2-en-1-one (IX) in ether - THF giving trimethylsilyl-9-oxo-11alpha,16-bistrimethylsilyloxy-16-vinyl-5-cis-13-trans-prostadienoate (X).The hydrolysis of (X) with acetic acid in THF-water yields 9-oxo-11alpha,16-dihydroxy-16-vinyl-5-cis-13-trans-prostadienoic acid (XI),which is finally methylated with diazomethane in ether.
合成路线:The oxidation of 1-hepten-3-ol (XII) with pyridinium chlorochromate gives 1-hepten-3-one (XIII),which by a Grignard condensation with propargylmagnesium bromide (XIV) is converted into 4-hydroxy-4-vinyl-1-octyne (XV).The protection of (XV) with trimethylsilyl chloride and imidazole in DMF yields 4-trimethylsilyloxy-4-vinyl-1-octyne (XVI),which by reaction with tri-n-butyl-stannane and azobisisobutyronitrile at 125 C affords 1-(tri-n-butylstannyl)-4-vinyl-4-(trimethylsilyloxy)-1-octene (XVII).Finally,this compound by reaction with butyllithium and copper -1-pentyne-tributylphosphine (C) in HMPT yields the copper salt (VIII),already obtained.
参考文献标题:CL-115,347
文献作者:Hillier,K.; Blancafort,P.; Serradell,M.N.; Castar,J.
参考来源:Drugs Fut 1983,8(4),307
合成路线:The oxidation of 1-hepten-3-ol (XII) with pyridinium chlorochromate gives 1-hepten-3-one (XIII),which by a Grignard condensation with propargylmagnesium bromide (XIV) is converted into 4-hydroxy-4-vinyl-1-octyne (XV).The protection of (XV) with trimethylsilyl chloride and imidazole in DMF yields 4-trimethylsilyloxy-4-vinyl-1-octyne (XVI),which by reaction with tri-n-butyl-stannane and azobisisobutyronitrile at 125 C affords 1-(tri-n-butylstannyl)-4-vinyl-4-(trimethylsilyloxy)-1-octene (XVII).Finally,this compound by reaction with butyllithium and copper -1-pentyne-tributylphosphine (C) in HMPT yields the copper salt (VIII),already obtained.
合成路线:The oxidation of 1-hepten-3-ol (XI) with pyridinium chlorochromate gives 1-hepten-3-one (XIII),which by a Grignard condensation with propargylmagnesium bromide (XIII) is converted to 4-hydroxy-4-vinyl-1-octyne (XIV).The protection of (XIV) with trimethylsilyl chloride and imidazole as before yields 4-trimethylsilyloxy-4-vinyl-1-octyne (XV),which by reaction with tri-n-butylstannane and azobisisobutyronitrile at 125 C affords 1-(tri-n-butylstannyl)-4-vinyl-4-(trimethylsilyloxy)-1-octene (XVI).Finally,this compound,by reaction with butyllithium and copper(I)-1-pentyne tributylphosphine as before yields the copper salt (VIII),which is condensed with 2-(6-trimethylsilyloxycarbonyl)-2-cis-hexenyl)-4-trime-thylsilyloxycyclopent-2-en-1-one (IX) in ether-THF giving trimethylsilyl-9-oxo-11 alpha,16-bis(trimethylsilyloxy)-16-vinyl-5-cis-13-trans-prostadienoate (X).Finally,this compound is hydrolyzed with acetic acid in THF water.
参考文献标题:Prostaglandins and congeners.29.(16RS)-Rac-15-deoxy-16-hydroxy-16-vivyl-protaglandin E2,an orally and transdermally active hypotensive agent of prolonged duration
文献作者:Bimbaum,J.E.; Cervoni,P.; Chan,P.S.; Chen,S.L.; Floyd,M.B.; Grudzinkas,C.V.; Weiss,M.J.; Dessy,F.
参考来源:J Med Chem 1982,25(5),492-494
产品链接: CAS No. 73621-92-8››