2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)acetaldehyde -Drug Synthesis Database

【结构式】

【分子编号】47724

【品名】2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)acetaldehyde

【CA登记号】

【分子式】C₂₁H₄₀O₃Si₂

【分子量】396.7178

【元素组成】C 63.58% H 10.16% O 12.1% Si 14.16%

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：(XV)

The oxidation of the ring A precursor alcohol (XIV) with Dess-Martin reagent gave rise to a mixture of aldehyde (XV) and its cyclic tautomer, the pyran derivative (XVI). Coupling of this mixture with the lithium anion of sulfone (XIII), followed by quenching with acetyl chloride, furnished the target beta-acetoxy sulfone adduct (XVII) accompanied by the silyl-acetyl exchange product (XVIII). Reductive cleavage of the phenylsulfonyl group by means of sodium amalgam yielded the desired O-triethylsilyl triene (XIX) along with some O-acetyl byproduct. Finally, desilylation of (XIX) with tetrabutylammonium fluoride provided the title triol derivative, which was separated from its C-25 acetate byproduct by flash chromatography.

参考文献中间体

合成目标

【1】 Marczak, S.; et al.; Synthesis and biological activity of the 1alpha,25-dihydroxyvitamin D3 diastereomer with unnatural configuration at the rings C/D side-chain moiety. Bioorg Med Chem Lett 2001, 11, 1, 63.

中间体序号	中间体编号	品名	分子式	供应商	用于合成
(XIII)	47723	(1S,3aS,4S,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyloctahydro-1H-inden-4-yl phenyl sulfone; ([(5S)-5-[(1S,3aS,4S,7aS)-7a-methyl-4-(phenylsulfonyl)octahydro-1H-inden-1-yl]-1,1-dimethylhexyl]oxy)(triethyl)silane	C₃₀H₅₂O₃SSi	详情	详情
(XIV)	47614	2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)-1-ethanol	C₂₁H₄₂O₃Si₂	详情	详情
(XV)	47724	2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)acetaldehyde	C₂₁H₄₀O₃Si₂	详情	详情
(XVI)	47725	tert-butyl(dimethyl)silyl (6R,8S)-6-[[tert-butyl(dimethyl)silyl]oxy]-5,6,7,8-tetrahydro-1H-isochromen-8-yl ether; tert-butyl[((6R,8S)-8-[[tert-butyl(dimethyl)silyl]oxy]-5,6,7,8-tetrahydro-1H-isochromen-6-yl)oxy]dimethylsilane	C₂₁H₄₀O₃Si₂	详情	详情
(XVII)	47726	1-[(1S,3aS,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyl-4-(phenylsulfonyl)octahydro-1H-inden-4-yl]-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl acetate	C₅₃H₉₄O₇SSi₃	详情	详情
(XVIII)	47727	(5S)-5-[(1S,3aS,7aS)-4-[1-(acetoxy)-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl]-7a-methyl-4-(phenylsulfonyl)octahydro-1H-inden-1-yl]-1,1-dimethylhexyl acetate	C₄₉H₈₂O₈SSi₂	详情	详情
(XIX)	47728	(5S)-5-[(1S,3aS,7aS)-4-[(E)-2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethylidene]-7a-methyloctahydro-4H-inden-1-yl]-1,1-dimethylhexyl triethylsilyl ether; [((1R,5S)-3-[(Z)-2-((1S,3aS,7aS)-1-[(1S)-1,5-dimethyl-5-[(triethylsilyl)oxy]hexyl]-7a-methyloctahydro-4H-inden-4-ylidene)ethylidene]-5-[[tert-butyl(dimethyl)silyl]oxy]-4-methylenecyclohexyl)oxy](tert-butyl)dimethylsilane	C₄₅H₈₆O₃Si₃	详情	详情

Extended Information