【结 构 式】 |
【分子编号】64170 【品名】allyl (2R,3S,4R,5R)-2-[({(2R,3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-[(Z)-11-octadecenoylamino]tetrahydro-2H-pyran-2-yl}oxy)methyl]-4-(decyloxy)-5-[(3-oxotetradecanoyl)amino]-6-[(Z)-1-propenyloxy]tetrahydro-2H-pyran-3-yl carbonate 【CA登记号】 |
【 分 子 式 】C79H141N2O18P 【 分 子 量 】1437.964982 【元素组成】C 65.99% H 9.88% N 1.95% O 20.03% P 2.15% |
合成路线1
该中间体在本合成路线中的序号:(XXXVIII)Monosaccharide (XXI) was activated as the trichloroacetimidate (XXXIV) upon treatment with trichloracetonitrile. Coupling between the protected monosaccharide (XXXIII) and imidate (XXXIV) using silver triflate as the coupling promoter produced the protected disaccharide adduct (XXXV). After reductive cleavage of the trichloroethyl carbamate protecting group of (XXXV), the resultant amine (XXXVI) was acylated with vaccenoyl chloride (XXXVII) giving amide (XXXVIII).
【1】 Kobayashi, S.; Kawata, T.; Christ, W.J.; Rossignol, D.P. (Eisai Co., Ltd.); Substd. liposaccharides useful in the treatment and prevention of endotoxemia. US 5750664; WO 9639411 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(XXI) | 64154 | 2,2,2-trichloroethyl (3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-2-hydroxy-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)tetrahydro-2H-pyran-3-ylcarbamate | C27H47Cl3NO11P | 详情 | 详情 | |
(XXXIII) | 64165 | allyl (2R,3S,4R,5R)-4-(decyloxy)-2-(hydroxymethyl)-5-[(3-oxotetradecanoyl)amino]-6-[(Z)-1-propenyloxy]tetrahydro-2H-pyran-3-yl carbonate | C37H65NO9 | 详情 | 详情 | |
(XXXIV) | 64166 | (3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-{[(2,2,2-trichloroethoxy)carbonyl]amino}tetrahydro-2H-pyran-2-yl 2,2,2-trichloroethanimidoate | C29H47Cl6N2O11P | 详情 | 详情 | |
(XXXV) | 64167 | allyl (2R,3S,4R,5R)-2-{[((2R,3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-{[(2,2,2-trichloroethoxy)carbonyl]amino}tetrahydro-2H-pyran-2-yl)oxy]methyl}-4-(decyloxy)-5-[(3-oxotetradecanoyl)amino]-6-[(Z)-1-propenyloxy]tetrahydro-2H-pyran-3-yl carbonate | C64H110Cl3N2O19P | 详情 | 详情 | |
(XXXVI) | 64168 | allyl (2R,3S,4R,5R)-2-({[(2R,3R,4R,5S,6R)-3-amino-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)tetrahydro-2H-pyran-2-yl]oxy}methyl)-4-(decyloxy)-5-[(3-oxotetradecanoyl)amino]-6-[(Z)-1-propenyloxy]tetrahydro-2H-pyran-3-yl carbonate | C61H109N2O17P | 详情 | 详情 | |
(XXXVII) | 64169 | (Z)-11-octadecenoyl chloride | C18H33ClO | 详情 | 详情 | |
(XXXVIII) | 64170 | allyl (2R,3S,4R,5R)-2-[({(2R,3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-[(Z)-11-octadecenoylamino]tetrahydro-2H-pyran-2-yl}oxy)methyl]-4-(decyloxy)-5-[(3-oxotetradecanoyl)amino]-6-[(Z)-1-propenyloxy]tetrahydro-2H-pyran-3-yl carbonate | C79H141N2O18P | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号:(XXXVIII)Hydrolysis of the enol ether group of (XXXVIII) with HF yielded (XXXIX), which was converted to phosphate (XL) by sequential phosphitylation with diallyl N,N-diisopropylphosphoramidite, followed by oxidation with m-chloroperbenzoic acid. The title disaccharide was finally obtained by palladium-catalyzed deprotection of the allyl phosphate and carbonate ester groups of (XL).
【1】 Kobayashi, S.; Kawata, T.; Christ, W.J.; Rossignol, D.P. (Eisai Co., Ltd.); Substd. liposaccharides useful in the treatment and prevention of endotoxemia. US 5750664; WO 9639411 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(XXXVIII) | 64170 | allyl (2R,3S,4R,5R)-2-[({(2R,3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-[(Z)-11-octadecenoylamino]tetrahydro-2H-pyran-2-yl}oxy)methyl]-4-(decyloxy)-5-[(3-oxotetradecanoyl)amino]-6-[(Z)-1-propenyloxy]tetrahydro-2H-pyran-3-yl carbonate | C79H141N2O18P | 详情 | 详情 | |
(XXXIX) | 64171 | allyl (2R,3S,4R,5R)-2-[({(2R,3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-[(Z)-11-octadecenoylamino]tetrahydro-2H-pyran-2-yl}oxy)methyl]-4-(decyloxy)-6-hydroxy-5-[(3-oxotetradecanoyl)amino]tetrahydro-2H-pyran-3-yl carbonate | C76H137N2O18P | 详情 | 详情 | |
(XL) | 64172 | allyl (2R,3S,4R,5R,6R)-6-{[bis(allyloxy)phosphoryl]oxy}-2-[({(2R,3R,4R,5S,6R)-5-{[bis(allyloxy)phosphoryl]oxy}-4-{[(3R)-3-methoxydecyl]oxy}-6-(methoxymethyl)-3-[(Z)-11-octadecenoylamino]tetrahydro-2H-pyran-2-yl}oxy)methyl]-4-(decyloxy)-5-[(3-oxotetradecanoyl)amino]tetrahydro-2H-pyran-3-yl carbonate | C82H146N2O21P2 | 详情 | 详情 |