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【结 构 式】 
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【分子编号】64628 【品名】tert-butyl({(1S,2E)-1-[2-({(2R,3R,4R,5S,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-iodobutyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-5-methyl-3,4-bis[(trimethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}methyl)-2-propenyl]-2,4-pentadienyl}oxy)dimethylsilane; tert-butyl(dimethyl)silyl (1S,2E)-1-[2-({(2R,3R,4R,5S,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-iodobutyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-5-methyl-3,4-bis[(trimethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}methyl)-2-propenyl]-2,4-pentadienyl ether 【CA登记号】 |
【 分 子 式 】C51H103IO8Si5 【 分 子 量 】1111.70599 【元素组成】C 55.1% H 9.34% I 11.42% O 11.51% Si 12.63% |
合成路线1
该中间体在本合成路线中的序号：(XL)The selective monodesilylation of (XXXVII) by means of NaOH gives the butanol derivative (XXXVIII),which is treated with TsCl, TEA and DMAP to yield the tosylate (XXXIX). The reaction of (XXXIX) with LiI and lutidine, followed by silylation of the remaining OH groups with Tms-OTf and lutidine affords the silylated iodobutyl derivative (XL), which is finally treated with triphenylphosphine and Li2CO3 in acetonitrile/benzene to provide the desired advanced intermediate phosphonium salt (XLI).
| 【1】 Smith, A.B. III; Lin, Q.; Doughty, V.A.; Zhuang, L.; McBriar, M.D.; Kerns, J.K.; Brook, C.S.; Murase, N.; Nakayama, K.; The spongistatins: Architecturally complex natural products - Part two: Synthesis of the C(29-51) subunit, fragment assembly, and final elaboration to (+)-spongistatin 2. Angew Chem. Int Ed 2001, 40, 1, 196. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXXVII) | 64625 | tert-butyl({(1S,2E)-1-[2-({(2R,3R,4R,5S,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-{[tert-butyl(diphenyl)silyl]oxy}butyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-5-methyl-3,4-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}methyl)-2-propenyl]-2,4-pentadienyl}oxy)dimethylsilane; tert-butyl(dimethyl)silyl (1S,2E)-1-[2-({(2R,3R,4R,5S,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-{[tert-butyl(diphenyl)silyl]oxy}butyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-5-methyl-3,4-bis[(triethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}methyl)-2-propenyl]-2,4-pentadienyl ether | C73H134O9Si6 | 详情 | 详情 | |
| (XXXVIII) | 64626 | (2R,3S,4R,5R,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-hydroxybutyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-2-((4S,5E)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-methylene-5,7-octadienyl)-5-methyltetrahydro-2H-pyran-3,4-diol | C45H88O9Si3 | 详情 | 详情 | |
| (XXXIX) | 64627 | 4-((2R,3S,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{(S)-[(2R,3R,4R,5S,6R)-6-((4S,5E)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-methylene-5,7-octadienyl)-4,5-dihydroxy-3-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-6-methoxy-3-methyltetrahydro-2H-pyran-2-yl)butyl 4-methylbenzenesulfonate | C52H94O11SSi3 | 详情 | 详情 | |
| (XL) | 64628 | tert-butyl({(1S,2E)-1-[2-({(2R,3R,4R,5S,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-iodobutyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-5-methyl-3,4-bis[(trimethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}methyl)-2-propenyl]-2,4-pentadienyl}oxy)dimethylsilane; tert-butyl(dimethyl)silyl (1S,2E)-1-[2-({(2R,3R,4R,5S,6R)-6-{(S)-[(2R,4S,5S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-(4-iodobutyl)-2-methoxy-5-methyltetrahydro-2H-pyran-2-yl][(triethylsilyl)oxy]methyl}-5-methyl-3,4-bis[(trimethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}methyl)-2-propenyl]-2,4-pentadienyl ether | C51H103IO8Si5 | 详情 | 详情 | |
| (XLI) | 64629 | [4-((2R,3S,4S,6R)-4-{[tert-butyl(dimethyl)silyl]oxy}-6-{(S)-{(2R,3S,4R,5R,6R)-6-((4S,5E)-4-{[tert-butyl(dimethyl)silyl]oxy}-2-methylene-5,7-octadienyl)-3-methyl-4,5-bis[(trimethylsilyl)oxy]tetrahydro-2H-pyran-2-yl}[(triethylsilyl)oxy]methyl}-6-methoxy-3-methyltetrahydro-2H-pyran-2-yl)butyl](triphenyl)phosphonium iodide | C69H118IO8PSi5 | 详情 | 详情 |