(3aR,7R,7aR)-7-(1-ethoxyethoxy)-4-(hydroxymethyl)-2,2-dimethyltetrahydro-1,3-benzodioxol-5(4H)-one -Drug Synthesis Database

【结构式】

【分子编号】59864

【品名】(3aR,7R,7aR)-7-(1-ethoxyethoxy)-4-(hydroxymethyl)-2,2-dimethyltetrahydro-1,3-benzodioxol-5(4H)-one

【CA登记号】

【分子式】C₁₄H₂₄O₆

【分子量】288.34096

【元素组成】C 58.32% H 8.39% O 33.29%

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：(XVI)

Hydrogenolysis of the isoxazoline ring of (XV) in the presence of Raney-nickel and boric acid generated the (hydroxymethyl)cyclohexanone (XVI). After hydroxyl group protection of (XVI) as the silyl ether (XVII), Peterson olefination of the ketone function of (XVII) with the lithium derivative of ethyl trimethylsilylacetate (XVIII) furnished the unsaturated ester (XIX). Desilylation of (XIX) gave the primary alcohol (XX), which was dehydrated to (XXI) by treatment with methanesulfonyl chloride and pyridine. The 1-(ethoxy)ethoxy protecting group of (XXI) was then replaced by a silyl ether (XXII) by acidic ketal hydrolysis, followed by treatment with tert-butyldiphenylsilyl chloride and imidazole. Subsequent acetonide (XXII) hydrolysis gave diol (XXIII), which was regioselectively mono-silylated providing intermediate (XXIV)

参考文献中间体

合成目标

【1】 Takahashi, T.; Shiono, M. (Kuraray Co., Ltd.); Cyclohexanetriol derivs.. EP 0503630 .

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XV)	59863	(3aR,4R,8bR)-2,2-dimethyl-3a,4,5,8,8a,8b-hexahydro[1,3]dioxolo[4,5-e][2,1]benzisoxazol-4-yl 1-ethoxyethyl ether; (3aR,4R,8bR)-4-(1-ethoxyethoxy)-2,2-dimethyl-3a,4,5,8,8a,8b-hexahydro[1,3]dioxolo[4,5-e][2,1]benzisoxazole	C₁₄H₂₃NO₅	详情	详情
(XVI)	59864	(3aR,7R,7aR)-7-(1-ethoxyethoxy)-4-(hydroxymethyl)-2,2-dimethyltetrahydro-1,3-benzodioxol-5(4H)-one	C₁₄H₂₄O₆	详情	详情
(XVII)	59865	(3aR,7R,7aR)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-7-(1-ethoxyethoxy)-2,2-dimethyltetrahydro-1,3-benzodioxol-5(4H)-one	C₂₀H₃₈O₆Si	详情	详情
(XVIII)	49044	ethyl 2-(trimethylsilyl)acetate	C₇H₁₆O₂Si	详情	详情
(XIX)	59867	ethyl 2-[(3aR,7R,7aR)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-7-(1-ethoxyethoxy)-2,2-dimethyltetrahydro-1,3-benzodioxol-5(4H)-ylidene]acetate	C₂₄H₄₄O₇Si	详情	详情
(XX)	59866	ethyl 2-[(3aR,7R,7aR)-7-(1-ethoxyethoxy)-4-(hydroxymethyl)-2,2-dimethyltetrahydro-1,3-benzodioxol-5(4H)-ylidene]acetate	C₁₈H₃₀O₇	详情	详情
(XXI)	59868	ethyl 2-[(3aR,7R,7aR)-7-(1-ethoxyethoxy)-2,2-dimethyl-4-methylenetetrahydro-1,3-benzodioxol-5(4H)-ylidene]acetate	C₁₈H₂₈O₆	详情	详情
(XXII)	59869	ethyl 2-[(3aR,7R,7aS)-7-{[tert-butyl(diphenyl)silyl]oxy}-2,2-dimethyl-4-methylenetetrahydro-1,3-benzodioxol-5(4H)-ylidene]acetate	C₃₀H₃₈O₅Si	详情	详情
(XXIII)	59870	ethyl 2-((3R,4S,5R)-5-{[tert-butyl(diphenyl)silyl]oxy}-3,4-dihydroxy-2-methylenecyclohexylidene)acetate	C₂₇H₃₄O₅Si	详情	详情
(XXIV)	59871	ethyl 2-((3R,4R,5R)-3,5-bis{[tert-butyl(diphenyl)silyl]oxy}-4-hydroxy-2-methylenecyclohexylidene)acetate	C₄₃H₅₂O₅Si₂	详情	详情

Extended Information