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【结 构 式】 
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【分子编号】41554 【品名】(2S,3S,4E,6E)-8-[(2R,5S,7R,8S)-2-butyl-2-((1S)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-propynyl)-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-2,6-dimethyl-4,6-octadiene-1,3-diol 【CA登记号】 |
【 分 子 式 】C32H56O5Si 【 分 子 量 】548.87914 【元素组成】C 70.02% H 10.28% O 14.57% Si 5.12% |
合成路线1
该中间体在本合成路线中的序号：(XXI)A new Wittig condensation of aldehyde (XV) with phosphorane (XVI) in refluxing benzene gives the diunsaturated ester (XVII), which is reduced with DIBAL to the corresponding alcohol, and oxidated with DMP yielding the aldehyde (XVIII). The condensation of (XVIII) with the chiral propionyloxazolidinethione (XIX) by means of Sn(OTf)2 and 1-ethylpiperidine in dichloromethane affords the adduct (XX), which is treated with NaBH4 in THF to eliminate the chiral auxiliary and afford diol (XXI). The metalation of (XXI) with Bu3SnH and a Pd catalyst gives the vinylstannane (XXII), which is desilylated with TBAF in THF yielding the trihydroxycompound (XXIII). The condensation of stannane (XXIII) with iodobutenoic ester (XXIV) by means of a Pd catalyst affords the diunsaturated ester (XXV), which is selectively disilylated with TBDMSCl and imidazole in hot DMF to provide the disilyl ether (XXVI).
| 【1】 Guzzupe, A.N.; et al.; Total synthesis of the epidermal growth factor inhibitor (-)-reveromycin B. J Org Chem 2001, 66, 7, 2382. |
| 【2】 Cuzzupe, A.N.; et al.; Total synthesis of (-)-reveromycin B. Org Lett 2000, 2, 2, 191. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XV) | 41549 | (E)-4-[(2R,5S,7R,8S)-2-butyl-2-((1S)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-propynyl)-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-2-methyl-2-butenal | n/a | C27H46O4Si | 详情 | 详情 |
| (XVI) | 14689 | Methyl (triphenylphosphoranylidene)acetate; (methoxycarbonylmethylene)triphenylphosphorane；Methyl 2-(triphenyl-lambda(5)-phosphanylidene)acetate | 2605-67-6 | C21H19O2P | 详情 | 详情 |
| (XVII) | 41550 | methyl (2E,4E)-6-[(2R,5S,7R,8S)-2-butyl-2-((1S)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-propynyl)-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-4-methyl-2,4-hexadienoate | n/a | C30H50O5Si | 详情 | 详情 |
| (XVIII) | 41551 | (2E,4E)-6-[(2R,5S,7R,8S)-2-butyl-2-((1S)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-propynyl)-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-4-methyl-2,4-hexadienal | C29H48O4Si | 详情 | 详情 | |
| (XIX) | 41552 | 1-[(4S)-4-isopropyl-2-thioxo-1,3-oxazolidin-3-yl]-1-propanone | C9H15NO2S | 详情 | 详情 | |
| (XX) | 41553 | (2R,3S,4E,6E)-8-[(2R,5S,7R,8S)-2-butyl-2-((1S)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-propynyl)-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-3-hydroxy-1-[(4S)-4-isopropyl-2-thioxo-1,3-oxazolidin-3-yl]-2,6-dimethyl-4,6-octadien-1-one | C38H63NO6SSi | 详情 | 详情 | |
| (XXI) | 41554 | (2S,3S,4E,6E)-8-[(2R,5S,7R,8S)-2-butyl-2-((1S)-1-[[tert-butyl(dimethyl)silyl]oxy]-2-propynyl)-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-2,6-dimethyl-4,6-octadiene-1,3-diol | C32H56O5Si | 详情 | 详情 | |
| (XXII) | 41555 | (2S,3S,4E,6E)-8-[(2R,5S,7R,8S)-2-butyl-2-[(1S,2E)-1-[[tert-butyl(dimethyl)silyl]oxy]-3-(tributylstannyl)-2-propenyl]-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-2,6-dimethyl-4,6-octadiene-1,3-diol | n/a | C44H84O5SiSn | 详情 | 详情 |
| (XXIII) | 41556 | (2S,3S,4E,6E)-8-[(2R,5S,7R,8S)-2-butyl-2-[(1S,2E)-1-hydroxy-3-(tributylstannyl)-2-propenyl]-8-methyl-1,6-dioxaspiro[4.5]dec-7-yl]-2,6-dimethyl-4,6-octadiene-1,3-diol | n/a | C38H70O5Sn | 详情 | 详情 |
| (XXIV) | 41557 | 2-(trimethylsilyl)ethyl (E)-3-iodo-2-butenoate | n/a | C9H17IO2Si | 详情 | 详情 |
| (XXV) | 41558 | 2-(trimethylsilyl)ethyl (2E,4E,6S)-6-[(2R,5S,7R,8S)-2-butyl-7-[(2E,4E,6S,7S)-6,8-dihydroxy-3,7-dimethyl-2,4-octadienyl]-8-methyl-1,6-dioxaspiro[4.5]dec-2-yl]-6-hydroxy-3-methyl-2,4-hexadienoate | n/a | C35H60O7Si | 详情 | 详情 |
| (XXVI) | 41559 | 2-(trimethylsilyl)ethyl (2E,4E,6S)-6-[(2R,5S,7R,8S)-7-((2E,4E,6S,7S)-6,8-bis[[tert-butyl(dimethyl)silyl]oxy]-3,7-dimethyl-2,4-octadienyl)-2-butyl-8-methyl-1,6-dioxaspiro[4.5]dec-2-yl]-6-hydroxy-3-methyl-2,4-hexadienoate | n/a | C47H88O7Si3 | 详情 | 详情 |