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【结 构 式】

【分子编号】67584

【品名】 

【CA登记号】 

【 分 子 式 】C27H46O4Si

【 分 子 量 】462.74534

【元素组成】C 70.08% H 10.02% O 13.83% Si 6.07%

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:(VI)

Protection of prasterone (I) with ethylene glycol (II) in the presence of p-TsOH in refluxing benzene gives the corresponding ketal (III), which is further protected as the 3-O-silyl ether (IV) by treatment with TBDMSCl and imidazole in DMF. Allylic oxidation of compound (IV) by means of CrO3 and 3,5-dimethylpyrazole in CH2Cl2 or using RuCl3 and t-BuOOH in cyclohexane/water affords enone (V), which by chemoselective 1,2-reduction with NaBH4 and CeCl3 in THF/MeOH provides (R)-alcohol (VI). Subsequent esterification of alcohol (VI) with Ac2O and DMAP in pyridine produces acetate (VII), which is subjected to double bond hydroboration with BH3·THF in THF and oxidative hydrolysis using H2O2 and NaOH to yield diol (VIII). Protection of diol (VIII) with Ac2O and DMAP in pyridine gives diacetate (IX), which is selectively deprotected at C-3 by treatment with TBAF in THF resulting in the 3-hydroxysteroid (X). Hydrolysis of diacetate (X) using NaOMe in MeOH affords compound (XI), which by deketalization by means of AcOH provides ketone (XII). Protection of the 6,7-diol (XII) with 2,2-dimethoxypropane (XIII) in the presence of CSA then gives acetonide (XIV), which is submitted to a Wittig reaction with CH3PPh3Br in the presence of t-BuOK in refluxing THF to give alkene (XV) .

1 Burgoyne, D.L., Shen, Y., Langlands, J.M., Rogers, C., Chau, J.H.-L., Piers, E., Salari, H. (Biolipox AB). 6,7-Oxygenated steroids and uses related thereto. EP 1304333; US 6046185; WO 1998002450; JP 2001503732.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(X) 67588 (3R,6S,7S,8S,9R,10S,13R,14R)-3-hydroxy-10,13-dimethylhexadecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolane]-6,7-diyl diacetate   C25H38O7 详情 详情
(I) 11713 Dehydroepiandrosterone;prasterone;(3S,8R,9S,10R,13S,14S)-3-Hydroxy-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydro-17H-cyclopenta[a]phenanthren-17-one 53-43-0 C19H28O2 详情 详情
(II) 11295 Polyethylene glycol;1,2-Ethanediol;Monoethylene glycol; Ethylene glycol 107-21-1 C2H6O2 详情 详情
(III) 67581 (3R,8S,9R,10S,13R,14R)-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolan]-3-ol   C21H32O3 详情 详情
(IV) 67582 tert-butyl(((3R,8S,9R,10S,13R,14R)-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolan]-3-yl)oxy)dimethylsilane   C27H46O3Si 详情 详情
(V) 67583 (3R,8S,9R,10S,13R,14R)-3-((tert-butyldimethylsilyl)oxy)-10,13-dimethyl-1,3,4,8,9,10,11,12,13,14,15,16-dodecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolan]-7(2H)-one   C27H44O4Si 详情 详情
(VI) 67584     C27H46O4Si 详情 详情
(VII) 67585 (3R,7S,8S,9R,10S,13R,14R)-3-((tert-butyldimethylsilyl)oxy)-10,13-dimethyl-1,2,3,4,7,8,9,10,11,12,13,14,15,16-tetradecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolan]-7-yl acetate   C29H48O5Si 详情 详情
(VIII) 67586 (3R,6S,7S,8S,9R,10S,13R,14R)-3-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolane]-6,7-diol   C27H48O5Si 详情 详情
(IX) 67587 (3R,6S,7S,8S,9R,10S,13R,14R)-3-((tert-butyldimethylsilyl)oxy)-10,13-dimethylhexadecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolane]-6,7-diyl diacetate   C31H52O7Si 详情 详情
(XI) 67589 (3R,6S,7S,8S,9R,10S,13R,14R)-10,13-dimethylhexadecahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolane]-3,6,7-triol   C21H34O5 详情 详情
(XII) 67590 (3R,6S,7S,8S,9R,10S,13R,14R)-3,6,7-trihydroxy-10,13-dimethyltetradecahydro-1H-cyclopenta[a]phenanthren-17(2H)-one   C19H30O4 详情 详情
(XIII) 67580 2,2-dimethoxypropane   C4H12O2 详情 详情
(XIV) 67591 (2R,4aS,4bR,6aR,9aR,9bS,9cS,12aS)-2-hydroxy-4a,6a,11,11-tetramethyltetradecahydro-1H-cyclopenta[1,2]phenanthro[9,10-d][1,3]dioxol-7(8H)-one   C22H34O4 详情 详情
Extended Information