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【结 构 式】

【分子编号】10664

【品名】[1-(Methoxymethoxy)vinyl]lithium

【CA登记号】

【 分 子 式 】C4H7LiO2

【 分 子 量 】94.03938

【元素组成】C 51.09% H 7.5% Li 7.38% O 34.03%

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:(XLVII)

2) The silylation of the hydroxyketal (XXXI) with TBDMS-Tf in dichloromethane gives the corresponding silyl ether (XXXII), which is treated sequentially with borane in THF, with H2O2 and tetrapropylammonium perruthenate catalyst to afford ketone (XXXIII). The reaction of (XXXIII) with KHMDS and TFNP in anhydrous THF yields the enol triflate (XXXIV), which by addition of CO catalyzed by triphenylphosphine and Pd(OAc)2 in methanol is converted to the methyl ester (XXXV). The reduction of (XXXV) with DIBAL in hexane gives the alcohol derivative (XXXVI), which by OsO4 oxidation in acetone/water gives the triol (XXXVII). The dehydration of (XXXVII) by previous silylation with TMS-Cl and reaction with trifluoromethanesulfonic anhydride in dichloromethane affords the oxetane derivative (XXXVIII), which is submitted to deketalization with CLTS to yield the ketone (XXXIX). The dehydrogenation of (XXXIX) by reaction with lithium diisopropylamide TMS-Cl and Pd(OAc)2 in THF gives the enone (XL), which is silylated with TBDMS-Cl in DMF to the fully silylated enone (XLI). The enolization of (XLI) with butyllithium and TMS-Cl followed by ozonolysis with O3 in dichloromethane yields the dialdehyde (XLII), which is submitted to a selective ketalization of the less hindered aldehyde group, affording the monoketal (XLIII). The addition of the lithium dithiane derivative (XLIV) to (XLIII) followed by a Swern oxidation of the intermediate alcohol gives the ketone (XLV), which is deketalized in acidic medium to yield the keto aldehyde (XLVI). The addition of the vinyllithium compound (XLVII) to (XLVI) gives the Diels-Alder precursor (XLVIII), which is submitted to cyclization by heating to afford the polycyclic compound (II) with the basic skeleton of paclitaxel.

1 Danishefsky, S.J.; Bornmann, W.G.; Queneau, Y.; Magee, T.V.; Krol, W.J. (Sloan-Kettering Institute); Total synthesis of taxol. US 5416225 .
中间体序号 中间体编号 品名 CAS号 分子式 供应商 用于合成
11295 Polyethylene glycol;1,2-Ethanediol;Monoethylene glycol; Ethylene glycol 107-21-1 C2H6O2 详情 详情
(IL) 10666 (2aR,4S,11S,12aR,12bS)-11-(Methoxymethyl)-4a,8,13,13-tetramethyl-4,12b-bis(tert-butyldimethylsilyloxy)-2a,3,4,4a,5,6,9,10,11,12,12a,12b-dodecahydro-1H-7,11-methanocyclodeca[3,4]benz[1,2-b]oxete-5,6,12-trione 6,6-propyleneditihoketal C37H64O7S2Si2 详情 详情
(XXXI) 10648 4'a-Methyl-3',4',4'a,5',6',7'-hexahydro-1'H-spiro[[1,3]dioxolane-2,2'-naphthalen]-5'-ol C13H20O3 详情 详情
(XXXII) 10649 tert-Butyl-dimethyl-(4'a-methyl-3',4',4'a,5',6',7'-hexahydro-1'H-spiro[[1,3]dioxolane-2,2'-naphthalen]-5'-yloxy)-silane C19H34O3Si 详情 详情
(XXXIII) 10650 5'-(tert-Butyl-dimethyl-silanyloxy)-4'a-methyl-octahydro-spiro[[1,3]dioxolane-2,2'-naphthalen]-8'-one C19H34O4Si 详情 详情
(XXXIV) 10651 Trifluoro-methanesulfonic acid 5'-(tert-butyl-dimethyl-silanyloxy)-4'a-methyl-3',4',4'a,5',6',8'a-hexahydro-1'H-spiro[[1,3]dioxolane-2,2'-naphthalen]-8'-yl ester C20H33F3O6SSi 详情 详情
(XXXV) 10652 5'-(tert-Butyl-dimethyl-silanyloxy)-4'a-methyl-3',4',4'a,5',6',8'a-hexahydro-1'H-spiro[[1,3]dioxolane-2,2'-naphthalene]-8'-carboxylic acid methyl ester C21H36O5Si 详情 详情
(XXXVI) 10653 (4aS,8aS)-8-(Hydroxymethyl)-4a-methyl-5-(tert-butyldimethylsilyloxy)-1,2,3,4,4a,5,6,8a-octahydronaphthalen-2-one ethyleneketal C20H36O4Si 详情 详情
(XXXVII) 10654 5'-(tert-Butyl-dimethyl-silanyloxy)-8'-hydroxymethyl-4'a-methyl-octahydro-spiro[[1,3]dioxolane-2,2'-naphthalene]-7',8'-diol C20H38O6Si 详情 详情
(XXXVIII) 10655 (2'aR,4'S,4'aS,8'aS)-4'a-Methyl-4'-(tert-butyldimethylsilyloxy)perhydrospiro[1,3-dioxolane-2,7'-naphtho[1,2-b]oxet]-8'b-ol C20H36O5Si 详情 详情
(XXXIX) 10656 (2aR,4S,4aS,8aS,8bS)-4-[[tert-butyl(dimethyl)silyl]oxy]-8b-hydroxy-4a-methyldecahydro-7H-naphtho[2,1-b]oxet-7-one C18H32O4Si 详情 详情
(XL) 10657 (2aR,4S,4aS,8aS,8bS)-4-[[tert-Butyl(dimethyl)silyl]oxy]-8b-hydroxy-4a-methyl-1,2a,3,4,4a,8,8a,8b-octahydro-7H-naphtho[2,1-b]oxet-7-one C18H30O4Si 详情 详情
(XLI) 10658 (2aR,4S,4aS,8aS,8bS)-4,8b-bis[[tert-Butyl(dimethyl)silyl]oxy]-4a-methyl-1,2a,3,4,4a,8,8a,8b-octahydro-7H-naphtho[2,1-b]oxet-7-one C24H44O4Si2 详情 详情
(XLII) 10659 (1S,2S,3S,4S,6R)-1,4-Bis[[tert-butyl(dimethyl)silyl]oxy]-3-methyl-7-oxabicyclo[4.2.0]octane-2,3-dicarbaldehyde C22H42O5Si2 详情 详情
(XLIII) 10660 (1S,2S,3S,4S,6R)-1,4-Bis[[tert-butyl(dimethyl)silyl]oxy]-2-(1,3-dioxolan-2-yl)-3-methyl-7-oxabicyclo[4.2.0]octane-3-carbaldehyde C24H46O6Si2 详情 详情
(XLIV) 10661 [2-(1-Isopropenyl-2-methyl-1-propenyl)-1,3-dithian-2-yl]lithium C11H17LiS2 详情 详情
(XLV) 10662 [(1S,2S,3S,4S,6R)-1,4-Bis[[tert-butyl(dimethyl)silyl]oxy]-2-(1,3-dioxolan-2-yl)-3-methyl-7-oxabicyclo[4.2.0]oct-3-yl][2-(1-isopropenyl-2-methyl-1-propenyl)-1,3-dithian-2-yl]methanone C35H62O6S2Si2 详情 详情
(XLVI) 10663 (1S,2S,3S,4S,6R)-1,4-Bis[[tert-butyl(dimethyl)silyl]oxy]-3-[[2-(1-isopropenyl-2-methyl-1-propenyl)-1,3-dithian-2-yl]carbonyl]-3-methyl-7-oxabicyclo[4.2.0]octane-2-carbaldehyde C33H58O5S2Si2 详情 详情
(XLVII) 10664 [1-(Methoxymethoxy)vinyl]lithium C4H7LiO2 详情 详情
(XLVIII) 10665 1-((1S,2S,3S,4S,6R)-1,4-Bis[[tert-butyl(dimethyl)silyl]oxy]-3-[[2-(1-isopropenyl-2-methyl-1-propenyl)-1,3-dithian-2-yl]carbonyl]-3-methyl-7-oxabicyclo[4.2.0]oct-2-yl)-2-(methoxymethoxy)-2-propen-1-one C37H64O7S2Si2 详情 详情
Extended Information