【结 构 式】 |
【分子编号】38693 【品名】[2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl](diphenyl)phosphine; tert-butyl(dimethyl)silyl (1R,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-5-[(E)-2-(diphenylphosphino)ethylidene]-4-methylenecyclohexyl ether 【CA登记号】 |
【 分 子 式 】C33H51O2PSi2 【 分 子 量 】566.911502 【元素组成】C 69.92% H 9.07% O 5.64% P 5.46% Si 9.91% |
合成路线1
该中间体在本合成路线中的序号:(XII)The tosylation of the primary alcohol of the hexahydroindenepropanol (I) with TsCl in pyridine gives the tosylate (II), which is treated with NaCN in DMSO to yield the butyronitrile (II). The reduction of (III) with diisobutylaluminum hydride in dichloromethane affords the butyraldehyde (IV), which is condensed with CBr4 by means of Zn in dichloromethane providing the 1,1-dibromo-1-pentene derivative (V). The dehydrobromination of (V) with n-BuLi in THF/hexane affords the 1-pentyne derivative (VI), which is treated with 1-(trimethylsilyl)imidazole to give the silyl ether (VII). The condensation of (VII) with acetone by means of n-BuLi in THF yields the 3-heptyn-2-ol derivative (VIII), which is desilylated with TBAF in THF affording the diol (IX). The oxidation of the secondary alcohol of (IX) with bipyridinium chlorochromate (BPCC) in dichloromethane provides the corresponding ketone (X), which is protected at the tertiary alcohol with 1-(trimethylsilyl)imidazole giving the silylated ketone (XI). The condensation of (XI) with the phosphorane (XII) by means of n-BuLi in THF yields the protected intermediate (XIII), which is finally deprotected with TBAF in THF.
【1】 Baggiolini, E.G.; Hennessy, B.M.; Shiuey, S.-J.; Truitt, G.A.; Uskokovic, M.R. (F. Hoffmann-La Roche AG); Dehydrocholecalciferol derivs.. AU 8928644; EP 0325279; JP 1990009861; US 5087619 . |
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) | 38682 | (3aS,7S,7aR)-3-[(1S)-2-hydroxy-1-methylethyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-ol | C13H22O2 | 详情 | 详情 | |
(II) | 38683 | (2S)-2-[(3aS,7S,7aR)-7-hydroxy-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl]propyl 4-methylbenzenesulfonate | C20H28O4S | 详情 | 详情 | |
(III) | 38684 | (3R)-3-[(3aS,7S,7aR)-7-hydroxy-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl]butanenitrile | C14H21NO | 详情 | 详情 | |
(IV) | 38685 | (3R)-3-[(3aS,7S,7aR)-7-hydroxy-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl]butanal | C14H22O2 | 详情 | 详情 | |
(V) | 38686 | (3aS,7S,7aR)-3-[(1R)-4,4-dibromo-1-methyl-3-butenyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-ol | C15H22Br2O | 详情 | 详情 | |
(VI) | 38687 | (3aS,7S,7aR)-3a-methyl-3-[(1R)-1-methyl-3-butynyl]-3a,4,5,6,7,7a-hexahydro-1H-inden-7-ol | C15H22O | 详情 | 详情 | |
(VII) | 38688 | (3aS,7S,7aR)-3a-methyl-3-[(1R)-1-methyl-3-butynyl]-3a,4,5,6,7,7a-hexahydro-1H-inden-7-yl trimethylsilyl ether; ([(3aS,7S,7aR)-3a-methyl-3-[(1R)-1-methyl-3-butynyl]-3a,4,5,6,7,7a-hexahydro-1H-inden-7-yl]oxy)(trimethyl)silane | C18H30OSi | 详情 | 详情 | |
(VIII) | 38689 | (6R)-6-[(3aS,7S,7aR)-3a-methyl-7-[(trimethylsilyl)oxy]-3a,4,5,6,7,7a-hexahydro-1H-inden-3-yl]-2-methyl-3-heptyn-2-ol | C21H36O2Si | 详情 | 详情 | |
(IX) | 38690 | (3aS,7S,7aR)-3-[(1R)-5-hydroxy-1,5-dimethyl-3-hexynyl]-3a-methyl-3a,4,5,6,7,7a-hexahydro-1H-inden-7-ol | C18H28O2 | 详情 | 详情 | |
(X) | 38691 | (3aR,7aS)-1-[(1R)-5-hydroxy-1,5-dimethyl-3-hexynyl]-7a-methyl-3,3a,5,6,7,7a-hexahydro-4H-inden-4-one | C18H26O2 | 详情 | 详情 | |
(XI) | 38692 | (3aR,7aS)-1-[(1R)-1,5-dimethyl-5-[(trimethylsilyl)oxy]-3-hexynyl]-7a-methyl-3,3a,5,6,7,7a-hexahydro-4H-inden-4-one | C21H34O2Si | 详情 | 详情 | |
(XII) | 38693 | [2-((3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylenecyclohexylidene)ethyl](diphenyl)phosphine; tert-butyl(dimethyl)silyl (1R,3S)-3-[[tert-butyl(dimethyl)silyl]oxy]-5-[(E)-2-(diphenylphosphino)ethylidene]-4-methylenecyclohexyl ether | C33H51O2PSi2 | 详情 | 详情 | |
(XIII) | 38694 | (5R)-5-[(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]-1,1-dimethyl-2-hexynyl trimethylsilyl ether; [((5R)-5-[(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]-1,1-dimethyl-2-hexynyl)oxy](trimethyl)silane | C42H74O3Si3 | 详情 | 详情 |