【结 构 式】 |
【分子编号】63140 【品名】tert-butyl(dimethyl)silyl 2-((2R,6R)-6-{(2S)-4-[(2S)-3-[(4-methoxybenzyl)oxy]-2-(methoxymethoxy)propyl]-2-methyl-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethyl ether; tert-butyl[2-((2R,6R)-6-{(2S)-4-[(2S)-3-[(4-methoxybenzyl)oxy]-2-(methoxymethoxy)propyl]-2-methyl-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethoxy]dimethylsilane 【CA登记号】 |
【 分 子 式 】C32H54O6Si 【 分 子 量 】562.86266 【元素组成】C 68.29% H 9.67% O 17.06% Si 4.99% |
合成路线1
该中间体在本合成路线中的序号:(XLV)The cleavage of the benzyl ether of (XXXVII) by means of Li/NH3, followed by treatment with I2 and PPh3 gives the iodide derivative (XXXVIII), which is condensed with tetrahydrofuranone (XXXIX) (obtained by reaction of epoxide (XL) with methyl 2-(phenylsulfonyl)acetate (XLI) and NaH) by means of NaH to afford the adduct (XLII). The reductive cleavage of the tetrahydrofuranone (XLII) by means of Red-Al provides the diol (XLIII), which is treated with Ph-COCl and Na/Hg to give the methylene derivative (XLIV). The reaction of (XLIV) with Mom-Cl and DIEA yields the Mom-ether compound (XLV), which is selectively deprotected by means of DDQ to afford the primary alcohol (XLVI). The oxidation of (XLVI) with oxalyl chloride provides the carbaldehyde (XLVII).
【1】 Ghosh, A.K.; Wang, Y.; Kim, J.T.; Total synthesis of microtubule-stabilizing agent (-)-laulimalide. J Org Chem 2001, 66, 26, 8973. |
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) | 63129 | benzyl (2R)-3-[(2S,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl ether; (2-{(2R,6S)-6-[(2R)-3-(benzyloxy)-2-methylpropyl]-5,6-dihydro-2H-pyran-2-yl}ethoxy)(tert-butyl)dimethylsilane | C24H40O3Si | 详情 | 详情 | |
(XXXVIII) | 63133 | tert-butyl(2-{(2R,6S)-6-[(2R)-3-iodo-2-methylpropyl]-5,6-dihydro-2H-pyran-2-yl}ethoxy)dimethylsilane; tert-butyl(dimethyl)silyl 2-{(2R,6S)-6-[(2R)-3-iodo-2-methylpropyl]-5,6-dihydro-2H-pyran-2-yl}ethyl ether | C17H33IO2Si | 详情 | 详情 | |
(XXXIX) | 63134 | (5S)-5-{[(4-methoxybenzyl)oxy]methyl}-3-(phenylsulfonyl)dihydro-2(3H)-furanone | C19H20O6S | 详情 | 详情 | |
(XL) | 63135 | 4-methoxybenzyl (2R)oxiranylmethyl ether; (2R)-2-{[(4-methoxybenzyl)oxy]methyl}oxirane | C11H14O3 | 详情 | 详情 | |
(XLI) | 63136 | methyl 2-(phenylsulfonyl)acetate | C9H10O4S | 详情 | 详情 | |
(XLII) | 63137 | (5S)-3-{(2R)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-5-{[(4-methoxybenzyl)oxy]methyl}-3-(phenylsulfonyl)dihydro-2(3H)-furanone | C36H52O8SSi | 详情 | 详情 | |
(XLIII) | 63138 | (4S)-2-{(2R)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-5-[(4-methoxybenzyl)oxy]-2-(phenylsulfonyl)-1,4-pentanediol | C36H56O8SSi | 详情 | 详情 | |
(XLIV) | 63139 | (2S)-4-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-1-[(4-methoxybenzyl)oxy]-4-penten-2-ol | C30H50O5Si | 详情 | 详情 | |
(XLV) | 63140 | tert-butyl(dimethyl)silyl 2-((2R,6R)-6-{(2S)-4-[(2S)-3-[(4-methoxybenzyl)oxy]-2-(methoxymethoxy)propyl]-2-methyl-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethyl ether; tert-butyl[2-((2R,6R)-6-{(2S)-4-[(2S)-3-[(4-methoxybenzyl)oxy]-2-(methoxymethoxy)propyl]-2-methyl-4-pentenyl}-5,6-dihydro-2H-pyran-2-yl)ethoxy]dimethylsilane | C32H54O6Si | 详情 | 详情 | |
(XLVI) | 63141 | (2S)-4-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-2-(methoxymethoxy)-4-penten-1-ol | C24H46O5Si | 详情 | 详情 | |
(XLVII) | 63142 | (2S)-4-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-2-(methoxymethoxy)-4-pentenal | C24H44O5Si | 详情 | 详情 |