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【结 构 式】

【分子编号】10632

【品名】(E)-5-[[tert-Butyl(dimethyl)silyl]oxy]-1-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-1-hydroxy-3-methyl-3-penten-2-one

【CA登记号】

【 分 子 式 】C29H54O6Si2

【 分 子 量 】554.91516

【元素组成】C 62.77% H 9.81% O 17.3% Si 10.12%

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)

1) The reaction of the known ketoketal (I) with N-phenyltrifluoromethanesulfonimide and KHMDS in THF gives the enol triflate (II), which is condensed with VIBuSn using tetrakis(triphenylphosphine)palladium(0) as catalyst in THF, yielding the diene (III). The reaction of (III) with 9-BBN in THF affords the alcohol (IV) and, after protection with TBDMS-Cl in dichloromethane, the silyl ether (V), which is oxidized with CrO3 and DMP in dichloromethane to the enone (VI). The stereoselective reduction of (VI) with BH3/THF catalyzed with the chiral borane (VII) yields the alcohol (VIII), which is protected with TBDMS-Cl as before to give (IX). Selective deprotection of (IX) affords the primary alcohol (X), which is oxidized with oxalyl chloride in DMSO to the aldehyde (XI). The condensation of (XI) with the vinyl iodide (XII) catalyzed by NiCl2 and CrCl2 gives the allyl alcohol (XIII), which is oxidized with oxalyl chloride as before to the enone (XIV). The oxidation of (XIV) with 3-phenyl-2-(phenylsulfonyl)oxaziridine and KHMDS yields the hydroxy ketone (XV), which is further oxidized with oxalyl chloride as before to afford the unsaturated dione (XVI). The Diels-Alder condensation between (XVI) and the diene (XVII) gives compound (XVIII) or (XIX), depending on the reaction conditions. The oxidation of the primary alcohol of (XIX) with oxalyl chloride as usual yields the aldehyde (XX), which by elimination of the ketal group in acidic medium affords the tetraketonic aldehyde (XXI).

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
(I) 10618 6,6,8-Trimethyl-1,4-dioxaspiro[4.5]decan-7-one C11H18O3 详情 详情
(II) 10619 6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl trifluoromethanesulfonate C12H17F3O5S 详情 详情
(III) 10620 6,6,8-Trimethyl-7-vinyl-1,4-dioxaspiro[4.5]dec-7-ene C13H20O2 详情 详情
(IV) 10621 6,6,8-Trimethyl-7-vinyl-1,4-dioxaspiro[4.5]dec-7-ene C13H20O2 详情 详情
(V) 10622 2-(6,6,8-Trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-1-ethanol C13H22O3 详情 详情
(VI) 10623 tert-Butyl(dimethyl)[2-(6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)ethoxy]silane; tert-Butyl(dimethyl)silyl 2-(6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)ethyl ether C19H36O3Si 详情 详情
(VII) 10624 (3aS)-1,3,3-Trimethyltetrahydro-3H-pyrrolo[1,2-c][1,3,2]oxazaborole C8H16BNO 详情 详情
(VIII) 10625 (7S)-9-(2-[[tert-Butyl(dimethyl)silyl]oxy]ethyl)-8,10,10-trimethyl-1,4-dioxaspiro[4.5]dec-8-en-7-ol C19H36O4Si 详情 详情
(IX) 10626 tert-Butyl(dimethyl)silyl (7S)-9-(2-[[tert-butyl(dimethyl)silyl]oxy]ethyl)-8,10,10-trimethyl-1,4-dioxaspiro[4.5]dec-8-en-7-yl ether; tert-Butyl[2-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)ethoxy]dimethylsilane C25H50O4Si2 详情 详情
(X) 10627 2-((9S)-9-[[tert-Butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-1-ethanol C19H36O4Si 详情 详情
(XI) 10628 2-((9S)-9-[[tert-Butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)acetaldehyde C19H34O4Si 详情 详情
(XII) 10629 tert-Butyl[[(E)-3-iodo-2-butenyl]oxy]dimethylsilane; tert-Butyl(dimethyl)silyl (E)-3-iodo-2-butenyl ether C10H21IOSi 详情 详情
(XIII) 10630 (E)-4-[[tert-Butyl(dimethyl)silyl]oxy]-1-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-3-methyl-3-buten-2-ol C28H54O5Si2 详情 详情
(XIV) 10631 (E)-5-[[tert-Butyl(dimethyl)silyl]oxy]-1-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-3-methyl-3-penten-2-one C29H54O5Si2 详情 详情
(XV) 10632 (E)-5-[[tert-Butyl(dimethyl)silyl]oxy]-1-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-1-hydroxy-3-methyl-3-penten-2-one C29H54O6Si2 详情 详情
(XVI) 10633 (E)-5-[[tert-Butyl(dimethyl)silyl]oxy]-1-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-3-methyl-3-pentene-1,2-dione C29H52O6Si2 详情 详情
(XVII) 10634 [(Z)-2-[(E)-2-(Benzyloxy)ethenyl]-4-(phenylsulfanyl)-2-butenyl](trimethyl)silane; Benzyl (1E,3Z)-5-(phenylsulfanyl)-3-[(trimethylsilyl)methyl]-1,3-pentadienyl ether C22H28OSSi 详情 详情
(XVIII) 10635 1-[(1S,2R,3S,6S)-6-(Benzyloxy)-2-([[tert-butyl(dimethyl)silyl]oxy]methyl)-1-methyl-4-oxo-3-[(phenylsulfanyl)methyl]cyclohexyl]-2-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-1,2-ethanedione C47H70O8SSi2 详情 详情
(XIX) 10636 1-[(1S,2R,3S,6S)-6-(Benzyloxy)-2-(hydroxymethyl)-1-methyl-4-oxo-3-[(phenylsulfanyl)methyl]cyclohexyl]-2-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-1,2-ethanedione C41H56O8SSi 详情 详情
(XX) 10637 (1R,2S,3S,6S)-3-(Benzyloxy)-2-[2-((9S)-9-[[tert-butyl(dimethyl)silyl]oxy]-6,6,8-trimethyl-1,4-dioxaspiro[4.5]dec-7-en-7-yl)-2-oxoacetyl]-2-methyl-5-oxo-6-[(phenylsulfanyl)methyl]cyclohexanecarbaldehyde C41H54O8SSi 详情 详情
(XXI) 10638 (1R,2S,3S,6S)-3-(Benzyloxy)-2-[2-[(3S)-3-hydroxy-2,6,6-trimethyl-5-oxo-1-cyclohexen-1-yl]-2-oxoacetyl]-2-methyl-5-oxo-6-[(phenylsulfanyl)methyl]cyclohexanecarbaldehyde C33H36O7S 详情 详情
Extended Information