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【结 构 式】

【分子编号】24526

【品名】(1'R,2'R,3'aR,6'aS)-2'-(Tetrahydropyranyloxy)spiro[1,3-dioxolane-2,5'-perhydropentalene]-1'-carbaldehyde

【CA登记号】

【 分 子 式 】C12H18O3

【 分 子 量 】210.27312

【元素组成】C 68.55% H 8.63% O 22.83%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(XI)

The decarboxylative hydrolysis ot 2beta,4alpha-di(methoxycarbonyl)-3alpha-(3-phenylpropyl)cyclopentanone (I) with HCl in refluxing acetic acid gives 3alpha-(3-phenylpropyl)cyclopentanone-4alpha-carboxylic acid methyl ester (II), which by successive reactions with oxalyl chloride in refluxing benzene, with diazomethane in ether, and with silver benzoate and triethylamine in methanol, is converted to 3alpha-(3-phenylpropyl)cyclopentanone-4alpha-acetic acid methyl ester (III). The dehydrogenation of (III) by reaction with N-bromosuccinimide and sodium selenobenzene in benzene and THF affords 3alpha-(3-phenyl-2-propenyl)cyclopentanone-4alpha-acetic acid methyl ester (IV), which is oxidized with sodium methaperiodate and Jones reagent, and methylated with diazomethane to give cyclopentanone 3alpha,4alpha-di(acetic acid) dimethyl ester (V). The reaction of (V) with ethyl eneglycol and p-toluenesulfonic acid yields the corresponding ketal (VI), which is submitted to a cyclization with sodium methoxide in hot methanol - DMSO to afford 7,7-ethylenedioxybicyclo[3.3.0] octan-3-one-4beta-carboxylic acid methyl ester (VII). The reduction of (VII) with NaBH4 in methanol gives the corresponding hydroxyester (VIII), which is protected with dihydropyran and p-toluenesulfonic acid to the corresponding tetrahydropyranyloxy compound (IX). The reduction of (IX) with LiAlH4 in ether affords the methanol derivative (X), which is oxidized with CrO3 - pyridine to the aldehyde (XI). The Wittig condensation of (XI) with dimethyl 2-oxo-4R,8-dimethyl-7-nonenylphosphonate (XII) by means of NaH in THF affords the dienic ketone (XIII).

1 Kojima, K.; Sakai, K.; Kobayashi, S. (Sankyo Co., Ltd.); Protacyclin compounds. DE 2900352; FR 2414039; GB 2012265; JP 54095552 .
2 Prous, J.; Castaner, J.; CS-570. Drugs Fut 1986, 11, 11, 918.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(I) 24516 methyl (1R,2S,3R)-3-acetyl-4-oxo-2-(3-phenylpropyl)cyclopentanecarboxylate C18H22O4 详情 详情
(II) 24517 methyl (1R,2S)-4-oxo-2-(3-phenylpropyl)cyclopentanecarboxylate C16H20O3 详情 详情
(III) 24518 methyl 2-[(1S,2S)-4-oxo-2-(3-phenylpropyl)cyclopentyl]acetate C17H22O3 详情 详情
(IV) 24519 methyl 2-[(1S,2S)-4-oxo-2-[(E)-3-phenyl-2-propenyl]cyclopentyl]acetate C17H20O3 详情 详情
(V) 24520 methyl 2-[(1R,2S)-2-(2-methoxy-2-oxoethyl)-4-oxocyclopentyl]acetate C11H16O5 详情 详情
(VI) 24521 methyl 2-[(7R,8S)-8-(2-methoxy-2-oxoethyl)-1,4-dioxaspiro[4.4]non-7-yl]acetate C13H20O6 详情 详情
(VII) 11312 (3'aS,4'R,6'aS)-5'-Oxoperhydrospiro[1,3-dioxolane-2,2'-pentalen]-4'-ylcarboxylic acid methyl ester C12H16O5 详情 详情
(VIII) 11313 (3'aS,4'R,5'R,6'aR)-5'-Hydroxyperhydrospiro[1,3-dioxolane-2,2'-pentalen]-4'-ylcarboxylic acid methyl ester C12H18O5 详情 详情
(IX) 24524 (1'R,2'R,3'aR,6'aS)-2'-(Tetrahydropyranyloxy)spiro[1,3-dioxolane-2,5'-perhydropentalene]-1'-carboxylic acid C17H26O6 详情 详情
(X) 24525 (1'R,2'R,3'aR,6'aS)-2'-(Tetrahydropyranyloxy)spiro[1,3-dioxolane-2,5'-perhydropentalene]-1'-methanol C16H26O5 详情 详情
(XI) 24526 (1'R,2'R,3'aR,6'aS)-2'-(Tetrahydropyranyloxy)spiro[1,3-dioxolane-2,5'-perhydropentalene]-1'-carbaldehyde C12H18O3 详情 详情
(XII) 63310 dimethyl (4R)-4,8-dimethyl-2-oxo-7-nonenylphosphonate C13H25O4P 详情 详情
(XIII) 24527 5(R),9-Dimethyl-1-[(2'(R),3'a(R),6'a(S))-2'-(tetrahydropyranyloxy)spiro[1,3-dioxolane-2,5'-perhydropentalen]-1-yl]deca-1(E),8-dien-3-one C27H42O5 详情 详情
Extended Information