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【结 构 式】 
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【分子编号】49658 【品名】diethyl (3R,5R,6Z,8Z,10E)-5-[[tert-butyl(dimethyl)silyl]oxy]-12-[[tert-butyl(diphenyl)silyl]oxy]-2-hydroxy-3-[(triethylsilyl)oxy]-6,8,10-dodecatrienylphosphonate 【CA登记号】 |
【 分 子 式 】C44H75O7PSi3 【 分 子 量 】831.305562 【元素组成】C 63.57% H 9.09% O 13.47% P 3.73% Si 10.14% |
合成路线1
该中间体在本合成路线中的序号：(XXV)The oxidation of alcohol (XXII) with DMP gives the corresponding aldehyde (XXIII), which is condensed with the lithium salt of diethyl methylphosphonate (XXIV), yielding the beta-hydroxy phosphonate (XXV). The oxidation of the OH group of (XXV) with DMP affords the corresponding ketone (XXVI), which is condensed with the already reported carbaldehyde intermediate (V) by means of potassium tert-butoxide to provide the adduct (XXVII). The methylation of the carbonyl group of (XXVII) with methyl lithium and CeCl3 gives tertiary alcohol (XXVIII), which is selectively monodesilylated with PPTS and ethanol (with simultaneous exchange of the isopropyl acetal group by an ethyl group), yielding the vicinal diol (XXIX). Under carefully controlled conditions, the monosilylation of the diol (XXIX) with Tbdms-OTf gives rise to tertiary silyl ether (XXX), which is treated with HCl to provide the lactol (XXXI). The oxidation of (XXXI) with silver carbonate affords the dihydropyranone (XXXII).
| 【1】 Boger, D.L.; et al.; Total synthesis of fostriecin (CI-920). J Am Chem Soc 2001, 123, 18, 4161. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (V) | 49639 | (2R)-6-isopropoxy-3,6-dihydro-2H-pyran-2-carbaldehyde | C9H14O3 | 详情 | 详情 | |
| (XXII) | 49655 | (2R,4R,5Z,7Z,9E)-4-[[tert-butyl(dimethyl)silyl]oxy]-11-[[tert-butyl(diphenyl)silyl]oxy]-2-[(triethylsilyl)oxy]-5,7,9-undecatrien-1-ol | C39H64O4Si3 | 详情 | 详情 | |
| (XXIII) | 49656 | (2R,4R,5Z,7Z,9E)-4-[[tert-butyl(dimethyl)silyl]oxy]-11-[[tert-butyl(diphenyl)silyl]oxy]-2-[(triethylsilyl)oxy]-5,7,9-undecatrienal | C39H62O4Si3 | 详情 | 详情 | |
| (XXIV) | 49657 | [(diethoxyphosphoryl)methyl]lithium | C5H12LiO3P | 详情 | 详情 | |
| (XXV) | 49658 | diethyl (3R,5R,6Z,8Z,10E)-5-[[tert-butyl(dimethyl)silyl]oxy]-12-[[tert-butyl(diphenyl)silyl]oxy]-2-hydroxy-3-[(triethylsilyl)oxy]-6,8,10-dodecatrienylphosphonate | C44H75O7PSi3 | 详情 | 详情 | |
| (XXVI) | 49659 | diethyl (3R,5R,6Z,8Z,10E)-5-[[tert-butyl(dimethyl)silyl]oxy]-12-[[tert-butyl(diphenyl)silyl]oxy]-2-oxo-3-[(triethylsilyl)oxy]-6,8,10-dodecatrienylphosphonate | C44H73O7PSi3 | 详情 | 详情 | |
| (XXVII) | 49660 | (1E,4R,6R,7Z,9Z,11E)-6-[[tert-butyl(dimethyl)silyl]oxy]-13-[[tert-butyl(diphenyl)silyl]oxy]-1-[(2R)-6-isopropoxy-3,6-dihydro-2H-pyran-2-yl]-4-[(triethylsilyl)oxy]-1,7,9,11-tridecatetraen-3-one | C49H76O6Si3 | 详情 | 详情 | |
| (XXVIII) | 49661 | (1E,3R,4R,6R,7Z,9Z,11E)-6-[[tert-butyl(dimethyl)silyl]oxy]-13-[[tert-butyl(diphenyl)silyl]oxy]-1-[(2R)-6-isopropoxy-3,6-dihydro-2H-pyran-2-yl]-3-methyl-4-[(triethylsilyl)oxy]-1,7,9,11-tridecatetraen-3-ol | C50H80O6Si3 | 详情 | 详情 | |
| (XXIX) | 49662 | (1E,3R,4R,6R,7Z,9Z,11E)-6-[[tert-butyl(dimethyl)silyl]oxy]-13-[[tert-butyl(diphenyl)silyl]oxy]-1-[(2R)-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]-3-methyl-1,7,9,11-tridecatetraene-3,4-diol | C43H64O6Si2 | 详情 | 详情 | |
| (XXX) | 49663 | (5R,6R,8R,9Z,11Z,13E)-8-[[tert-butyl(dimethyl)silyl]oxy]-5-[(E)-2-[(2R)-6-ethoxy-3,6-dihydro-2H-pyran-2-yl]ethenyl]-2,2,3,3,5,18,18-heptamethyl-17,17-diphenyl-4,16-dioxa-3,17-disila-9,11,13-nonadecatrien-6-ol | C49H78O6Si3 | 详情 | 详情 | |
| (XXXI) | 49664 | (5R,6R,8R,9Z,11Z,13E)-8-[[tert-butyl(dimethyl)silyl]oxy]-5-[(E)-2-[(2R)-6-hydroxy-3,6-dihydro-2H-pyran-2-yl]ethenyl]-2,2,3,3,5,18,18-heptamethyl-17,17-diphenyl-4,16-dioxa-3,17-disila-9,11,13-nonadecatrien-6-ol | C47H74O6Si3 | 详情 | 详情 | |
| (XXXII) | 49665 | (6R)-6-((1E,3R,4R,6R,7Z,9Z,11E)-3,6-bis[[tert-butyl(dimethyl)silyl]oxy]-13-[[tert-butyl(diphenyl)silyl]oxy]-4-hydroxy-3-methyl-1,7,9,11-tridecatetraenyl)-5,6-dihydro-2H-pyran-2-one | C47H72O6Si3 | 详情 | 详情 |