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【结 构 式】

【分子编号】63142

【品名】(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

【CA登记号】

【 分 子 式 】C24H44O5Si

【 分 子 量 】440.69586

【元素组成】C 65.41% H 10.06% O 18.15% Si 6.37%

与该中间体有关的原料药合成路线共 2 条

合成路线1

该中间体在本合成路线中的序号:(XLVII)

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

合成路线2

该中间体在本合成路线中的序号:(XLVII)

The condensation of carbaldehyde (XLVII) with the intermediate Pmb-protected phenyl sulfone (XXIII) by means of BuLi, Ac2O and Na/Hg gives the linear adduct (XLVIII), which is protected at its free OH group by means of DHP and PPTS, and selectively deprotected with TBAF yielding the primary alcohol (XLIX). The oxidation of (XLIX) with DMP affords the acetaldehyde derivative (L), which is condensed with CBr4 and PPh3 to provide the dibromovinyl derivative (LI). The condensation of (LI) with methyl chloroformate (LII) by means of BuLi gives the acetylenic ester (LIII), which is treated with CSA to eliminate the THP protecting group and yield the hydroxy ester (LIV). The hydrolysis of the ester (LIV) with LiOH in THF/water affords the hydroxyacid (LV).

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
(XXIII) 63121 (3S,4S,5E)-4-[(4-methoxybenzyl)oxy]-6-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-1-(phenylsulfonyl)-5-hexen-3-ol C26H32O6S 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
(XLVIII) 63143 (1E,3S,4S,6E,8S)-10-{(2S)-3-[(2R,6R)-6-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-3-[(4-methoxybenzyl)oxy]-8-(methoxymethoxy)-1-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-1,6,10-undecatrien-4-ol C44H70O8Si 详情 详情
(XLIX) 63144 2-{(2R,6R)-6-[(2S,6S,7E,10S,11S,12E)-11-[(4-methoxybenzyl)oxy]-6-(methoxymethoxy)-2-methyl-13-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-methylene-10-(tetrahydro-2H-pyran-2-yloxy)-7,12-tridecadienyl]-5,6-dihydro-2H-pyran-2-yl}-1-ethanol C43H64O9 详情 详情
(L) 63145 2-{(2R,6R)-6-[(2S,6S,7E,10S,11S,12E)-11-[(4-methoxybenzyl)oxy]-6-(methoxymethoxy)-2-methyl-13-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-methylene-10-(tetrahydro-2H-pyran-2-yloxy)-7,12-tridecadienyl]-5,6-dihydro-2H-pyran-2-yl}acetaldehyde C43H62O9 详情 详情
(LI) 63146 (1S,3E,5S)-7-{(2S)-3-[(2R,6R)-6-(3,3-dibromo-2-propenyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-1-{(1S,2E)-1-[(4-methoxybenzyl)oxy]-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-5-(methoxymethoxy)-3,7-octadienyl tetrahydro-2H-pyran-2-yl ether 2-{[(1S,3E,5S)-7-{(2S)-3-[(2R,6R)-6-(3,3-dibromo-2-propenyl)-3,6-dihydro-2H-pyran-2-yl]-2-methylpropyl}-1-{(1S,2E)-1-[(4-methoxybenzyl)oxy]-3-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-2-propenyl}-5-(methoxymethoxy)-3,7-octadienyl]oxy}tetrahydro-2H-pyran C44H62Br2O8 详情 详情
(LII) 16993 methyl chlorocarbonate;Carbonochloridic acid methyl ester;[(chlorocarbonyl)oxy]methane;methyl chloroformate 79-22-1 C2H3ClO2 详情 详情
(LIII) 63147 methyl 4-{(2R,6R)-6-[(2S,6S,7E,10S,11S,12E)-11-[(4-methoxybenzyl)oxy]-6-(methoxymethoxy)-2-methyl-13-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-methylene-10-(tetrahydro-2H-pyran-2-yloxy)-7,12-tridecadienyl]-5,6-dihydro-2H-pyran-2-yl}-2-butynoate C46H64O10 详情 详情
(LIV) 63148 methyl 4-((2R,6R)-6-{(2S,6S,7E,10S,11S,12E)-10-hydroxy-11-[(4-methoxybenzyl)oxy]-6-(methoxymethoxy)-2-methyl-13-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-methylene-7,12-tridecadienyl}-5,6-dihydro-2H-pyran-2-yl)-2-butynoate C41H56O9 详情 详情
(LV) 63149 4-((2R,6R)-6-{(2S,6S,7E,10S,11S,12E)-10-hydroxy-11-[(4-methoxybenzyl)oxy]-6-(methoxymethoxy)-2-methyl-13-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-4-methylene-7,12-tridecadienyl}-5,6-dihydro-2H-pyran-2-yl)-2-butynoic acid C40H54O9 详情 详情
Extended Information