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【结 构 式】

【分子编号】34604

【品名】(1S,5R)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol

【CA登记号】

【 分 子 式 】C34H58O2Si

【 分 子 量 】526.91882

【元素组成】C 77.5% H 11.09% O 6.07% Si 5.33%

与该中间体有关的原料药合成路线共 2 条

合成路线1

该中间体在本合成路线中的序号:(XXVII)

The silylation of vitamin D2 (XXIII) with TBDMS-Cl and imidazole in dichloromethane gives the silyl ether (XXIV), which is cyclized with N-sulfinyl-p-toluenesulfonamide yielding the Diels-Alder adduct (XXV). The oxidation of (XXV) with SeO2 and N-methylmorpholine-oxide in ethanol affords the trans-1alpha-hydroxy-3-O-(tert-butyldimethylsilyl)vitamin D2 (XXVI), which is irradiated with UV light in benzene containing anthracene yielding 1alpha-hydroxy-3-O-(tert-butyldimethylsilyl)vitamin D2 (XXVII). Finally, this compound is desilylated with TBAF in THF. The cyclization of the silyl ether (XXIV) can also be performed with Ts-N=Se=N-Ts yielding the corresponding adduct (XXVIII), which is oxidized with SeO2 as before to afford the trans-1alpha-hydroxy-3-O-(tert-butyldimethylsilyl) vitamin D2 (XXVI) already reported.

1 Guo, L.; Moriarty, R.M.; Penmasta, R.A. (Lunar Corp.); Synthesis of 1alpha-hydroxy vitamin D. WO 9602501 .
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XXIII) 12425 (1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexanol 50-14-6 C28H44O 详情 详情
(XXIV) 34603 [[(1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl]oxy](tert-butyl)dimethylsilane; (1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl tert-butyl(dimethyl)silyl ether C34H58OSi 详情 详情
(XXV) 34600 (5S)-4-([(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]methyl)-5-[[tert-butyl(dimethyl)silyl]methyl]-3-[(4-methylphenyl)sulfonyl]-3,4,5,6,7,8-hexahydro-2lambda(4),3-benzothiazin-2(1H)-one C42H67NO3S2Si 详情 详情
(XXVI) 34601 (1S,5R)-3-((E)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol C34H58O2Si 详情 详情
(XXVII) 34604 (1S,5R)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol C34H58O2Si 详情 详情
(XXVIII) 34599 N-[(5S)-4-([(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]methyl)-5-[[tert-butyl(dimethyl)silyl]methyl]-3-[(4-methylphenyl)sulfonyl]-3,4,5,6,7,8-hexahydro-2lambda(4),3-benzoselenazin-2(1H)-ylidene]-4-met C49H74N2O4S2SeSi 详情 详情

合成路线2

该中间体在本合成路线中的序号:(XXVII)

 

1 Andrews DR, Barton DHR, et aL. 1986.A direct, regio- and stereoselective lα-rhydroxylation of (5E-calciferol derivatives.J Org Chem, 51: 1635~1637
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(XXIII) 12425 (1S)-3-((Z)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexanol 50-14-6 C28H44O 详情 详情
(XXVI) 34601 (1S,5R)-3-((E)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol C34H58O2Si 详情 详情
(XXVII) 34604 (1S,5R)-3-((Z)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-5-[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexanol C34H58O2Si 详情 详情
(XXIX) 34605 (1S)-3-((E)-2-[(1R,3aR,7aR)-7a-methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexanol C28H44O 详情 详情
(XXXI) 12428 (1S)-3-((E)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl tert-butyl(dimethyl)silyl ether; [[(1S)-3-((E)-2-[(1R,3aR,7aR)-7a-Methyl-1-[(1R,2E,4R)-1,4,5-trimethyl-2-hexenyl]octahydro-4H-inden-4-ylidene]ethylidene)-4-methylenecyclohexyl]oxy](tert-butyl)dimethylsilane C34H58OSi 详情 详情
Extended Information