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【结 构 式】 
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【分子编号】61161 【品名】(1R,7S,11S,15S,17S)-7-{(1S,2E)-1-(methoxymethoxy)-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-15-methyl-13-methylene-11-{[(1R)-1-methyl-2-oxopropyl]oxy}-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one 【CA登记号】 |
【 分 子 式 】C36H52O8 【 分 子 量 】612.80408 【元素组成】C 70.56% H 8.55% O 20.89% |
合成路线1
该中间体在本合成路线中的序号：(XL)The condensation of the dihydropyranyl acetaldehyde intermediate (XVII) with the phosphonate (XXXVII) by means of KHMDS gives the open chain adduct (XXXVIII), which is cyclized by means of EtAlCl2 in dichloromethane to yield the macrolactone (XXXIX). The oxidation of the secondary OH group of (XXXIX) by means of DMP affords the ketone (XL), which is treated with TsOH in chloroform to provide the alcohol (XLI). The deprotection of the Mom-protecting group by means of Me2BBr in dichloromethane gives the dihydroxylated macrolactone (XLII), which is finally epoxidized by means of (+)-DIPT, t-BuOOH and Ti(i-PrO)4 to yield the target Laulimalide.
| 【1】 Ahmed, A.; Hoegenauer, E.K.; Enev, V.S.; Hanbauer, M.; Kaehlig, H.; Ohler, E.; Mulzer, J.; Total synthesis of the microtubule stabilizing antitumor agent laulimalide and some nonnatural analogues: The power of Sharpless' asymmetric epoxidation. J. Org. Chem. 2003, 68, 8, 3026. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XVII) | 61140 | 2-((2R,6S)-6-{(2S)-2-methyl-4-[(trimethylsilyl)methyl]-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)acetaldehyde | C17H30O2Si | 详情 | 详情 | |
| (XXXVII) | 61158 | (1S,2S,3E)-1-{(E)-3-[(4R,6R)-4,6-dimethyl-1,3-dioxan-2-yl]-2-propenyl}-2-(methoxymethoxy)-4-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-3-butenyl 2-[bis(2,2,2-trifluoroethoxy)phosphoryl]acetate | C27H39F6O10P | 详情 | 详情 | |
| (XXXVIII) | 61159 | (1S,2S,3E)-1-{(E)-3-[(4R,6R)-4,6-dimethyl-1,3-dioxan-2-yl]-2-propenyl}-2-(methoxymethoxy)-4-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-3-butenyl (Z)-4-((2R,6S)-6-{(2S)-2-methyl-4-[(trimethylsilyl)methyl]-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)-2-buten | C40H64O8Si | 详情 | 详情 | |
| (XXXIX) | 61160 | (1R,7S,11S,15S,17S)-11-{[(1R,2S)-2-hydroxy-1-methylpropyl]oxy}-7-{(1S,2E)-1-(methoxymethoxy)-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-15-methyl-13-methylene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one | C36H54O8 | 详情 | 详情 | |
| (XL) | 61161 | (1R,7S,11S,15S,17S)-7-{(1S,2E)-1-(methoxymethoxy)-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-15-methyl-13-methylene-11-{[(1R)-1-methyl-2-oxopropyl]oxy}-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one | C36H52O8 | 详情 | 详情 | |
| (XLI) | 61162 | +(1R,7S,11S,15S,17S)-11-hydroxy-7-{(1S,2E)-1-(methoxymethoxy)-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-15-methyl-13-methylene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one | C32H46O7 | 详情 | 详情 | |
| (XLII) | 61163 | (1R,7S,11S,15S,17S)-11-hydroxy-7-{(1S,2E)-1-hydroxy-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-15-methyl-13-methylene-6,21-dioxabicyclo[15.3.1]henicosa-3,9,19-trien-5-one | C30H42O6 | 详情 | 详情 |