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【结 构 式】 
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【分子编号】57667 【品名】(3aR,7aS)-7a-methyl-1-[(1R)-1,6,6-trimethyl-5-oxoheptyl]-3,3a,5,6,7,7a-hexahydro-4H-inden-4-one 【CA登记号】 |
【 分 子 式 】C20H32O2 【 分 子 量 】304.47288 【元素组成】C 78.9% H 10.59% O 10.51% |
合成路线1
该中间体在本合成路线中的序号：(V)Alkylation of the lithium enolate of pinacolone (II) with alkyl iodide (I) affords ketone (III). After desilylation of (III) by means of tetrabutylammonium fluoride, the resultant alcohol (IV) is oxidized to the corresponding ketone (V) employing N-methylmorpholine-N-oxide in the presence of a catalytic amount of tetrapropylammonium perruthenate. Wadsworth-Emmons condensation of ketone (V) with the racemic phosphine oxide (VI) provides a diastereomeric mixture of diene adducts (VII). After conversion of (VII) to the corresponding oxime, the desired isomer (VIII) is isolated by column chromatography. Finally, desilylation of (VIII) by means of tetrabutylammonium fluoride provides the title compound.
| 【1】 Posner, G.H.; Kensler, T.W.; Dolan, P.; Peleg, S.; Halford, B.A.; Conceptually new low-calcemic oxime analogues of the hormone 1alpha,25-dihydroxyvitamin D3: Synthesis and biological testing. J Med Chem 2002, 45, 8, 1723. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VIIa) | 57668 | (7R)-7-{(3aS,7aS)-7-[(E)-2-((3S,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-2-methylenecyclohexylidene)ethylidene]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl}-2,2-dimethyl-3-octanone | C41H72O3Si2 | 详情 | 详情 | |
| (VIIb) | 57669 | (7R)-7-{(3aS,7aS)-7-[(E)-2-((3R,5S)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-2-methylenecyclohexylidene)ethylidene]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl}-2,2-dimethyl-3-octanone | C41H72O3Si2 | 详情 | 详情 | |
| (I) | 42570 | ([(3aS,7S,7aR)-3-[(1R)-3-iodo-1-methylpropyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-yl]oxy)(triethyl)silane; (3aS,7S,7aR)-3-[(1R)-3-iodo-1-methylpropyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-yl triethylsilyl ether | C20H37IOSi | 详情 | 详情 | |
| (II) | 10128 | 3,3-Dimethyl-2-butanone; Pinacolin | 75-97-8 | C6H12O | 详情 | 详情 |
| (III) | 57651 | (7R)-7-{(3aS,7S,7aR)-3a-methyl-7-[(triethylsilyl)oxy]-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl}-2,2-dimethyl-3-octanone | C26H48O2Si | 详情 | 详情 | |
| (IV) | 57666 | (7R)-7-[(3aS,7S,7aR)-7-hydroxy-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl]-2,2-dimethyl-3-octanone | C20H34O2 | 详情 | 详情 | |
| (V) | 57667 | (3aR,7aS)-7a-methyl-1-[(1R)-1,6,6-trimethyl-5-oxoheptyl]-3,3a,5,6,7,7a-hexahydro-4H-inden-4-one | C20H32O2 | 详情 | 详情 | |
| (VI) | 42574 | [2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl](oxo)diphenylphosphorane; 2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl(diphenyl)phosphine oxide | C33H51O3PSi2 | 详情 | 详情 | |
| (VIII) | 57670 | (7R)-7-{(3aS,7aS)-7-[(E)-2-((3S,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}-2-methylenecyclohexylidene)ethylidene]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl}-2,2-dimethyl-3-octanone oxime | C41H73NO3Si2 | 详情 | 详情 |