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【结 构 式】

【分子编号】57143

【品名】(1R,5R)-3-(bromomethylene)-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl tert-butyl(dimethyl)silyl ether; [((1R,5R)-3-(bromomethylene)-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl)oxy](tert-butyl)dimethylsilane

【CA登记号】

【 分 子 式 】C19H39BrO2Si2

【 分 子 量 】435.59246

【元素组成】C 52.39% H 9.02% Br 18.34% O 7.35% Si 12.9%

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)

The reaction of the chiral cyclohexenone (I) with H2O2 and NaOH in methanol gives the epoxide (II), which is submitted to a Wittig olefination with the phosphonium bromide (III) and KHMDS in toluene to yield the bromomethylene derivative (IV). The opening of the epoxide ring by means of DIBAL in hexane affords the cyclohexanol (V), which is silylated with Tbdms-Cl and imidazole to provide the bis silyl ether (VI). The reaction of (VI), triisopropyl borate and pinacol by means of t-BuLi in ethyl ether gives the boronic ester (VII), which is condensed with alkyl bromide intermediate (VIII) and catalyzed by PdCl2(dppf) and KOH in THF/water to yield the silylated precursor (IX). Finally, this compound is desilylated by means of aq. HF in THF to provide the target 1-alpha,25-dihydroxy-19-nor-vitamin D3. Alternatively, the intermediate (VIII) is reacted with triisiopropyl borate and pinacol, as before, to give the boronic ester (X), which is condensed with the cyclohexylidenemethyl bromide (VI) and catalyzed by PdCl2(dppf) and KOH in THF/water to yield the already reported silylated precursor (IX).

1 Hanazawa, T.; et al.; Novel synthetic approach to 19-nor-1alpha,25-dihydroxyvitamin D3 and its derivatives by Suzuki-Miyaura coupling in solution and on solid support. Org Lett 2001, 3, 24, 3975.
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
(I) 57138 (5S)-5-{[tert-butyl(dimethyl)silyl]oxy}-2-cyclohexen-1-one C12H22O2Si 详情 详情
(II) 57139 (1S,4S,6S)-4-{[tert-butyl(dimethyl)silyl]oxy}-7-oxabicyclo[4.1.0]heptan-2-one C12H22O3Si 详情 详情
(III) 57140 (bromomethyl)(trimethyl)phosphonium bromide C4H11Br2P 详情 详情
(IV) 57141 ({(1S,3R,6R)-5-[(E)-bromomethylidene]-7-oxabicyclo[4.1.0]hept-3-yl}oxy)(tert-butyl)dimethylsilane; (1S,3R,6R)-5-[(E)-bromomethylidene]-7-oxabicyclo[4.1.0]hept-3-yl tert-butyl(dimethyl)silyl ether C13H23BrO2Si 详情 详情
(V) 57142 (1R,5R)-3-[(Z)-bromomethylidene]-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexanol C13H25BrO2Si 详情 详情
(VI) 57143 (1R,5R)-3-(bromomethylene)-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl tert-butyl(dimethyl)silyl ether; [((1R,5R)-3-(bromomethylene)-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl)oxy](tert-butyl)dimethylsilane C19H39BrO2Si2 详情 详情
(VII) 57144 tert-butyl(dimethyl)silyl (1R,3R)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylene]cyclohexyl ether; tert-butyl({(1R,3R)-3-{[tert-butyl(dimethyl)silyl]oxy}-5-[(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylene]cyclohexyl}oxy)dimethylsilane C25H51BO4Si2 详情 详情
(VIII) 57145 (5R)-5-{(1R,7aR)-4-[(E)-bromomethylidene]-7a-methyloctahydro-1H-inden-1-yl}-1,1-dimethylhexyl trimethylsilyl ether; [((5R)-5-{(1R,7aR)-4-[(E)-bromomethylidene]-7a-methyloctahydro-1H-inden-1-yl}-1,1-dimethylhexyl)oxy](trimethyl)silane C22H41BrOSi 详情 详情
(IX) 57147 [((1R,5R)-3-[2-((1R,7aR)-1-{(1R)-1,5-dimethyl-5-[(trimethylsilyl)oxy]hexyl}-7a-methyloctahydro-4H-inden-4-ylidene)ethylidene]-5-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl)oxy](tert-butyl)dimethylsilane; (5R)-5-{(1R,7aR)-4-[(E)-2-((3R,5R)-3,5-bis{[tert-butyl(dimethyl)silyl]oxy}cyclohexylidene)ethylidene]-7a-methyloctahydro-4H-inden-1-yl}-1,1-dimethylhexyl trimethylsilyl ether C41H80O3Si3 详情 详情
(X) 57146 (5R)-5-{(1R,7aR)-7a-methyl-4-[(E)-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylidene]octahydro-1H-inden-1-yl}-1,1-dimethylhexyl trimethylsilyl ether; [((5R)-5-{(1R,7aR)-7a-methyl-4-[(E)-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methylidene]octahydro-1H-inden-1-yl}-1,1-dimethylhexyl)oxy](trimethyl)silane C28H53BO3Si 详情 详情
Extended Information