【结 构 式】 |
【分子编号】58158 【品名】(4aS,6R,7R,8R,8aS)-6-({(2R,3S,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-8-methoxy-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-ol 【CA登记号】 |
【 分 子 式 】C32H44O11 【 分 子 量 】604.69476 【元素组成】C 63.56% H 7.33% O 29.1% |
合成路线1
该中间体在本合成路线中的序号:(XXVIII)Preparation of the tetrasaccharide building block (XXXIV) is carried out as follows. The disaccharide benzoate ester (XXVII) is hydrolyzed to alcohol (XXVIII), which is subsequently alkylated with iodomethane and NaH to the methyl ether (XXIX). Acidic hydrolysis of the acetonide group of (XXIX) provides diol (XXX). The primary alcohol of (XXX) is then oxidized by means of TEMPO and NaOCl, yielding carboxylic acid (XXXI), which is further converted to the benzyl ester (XXXII) upon treatment with benzyl bromide and KHCO3. Coupling of the disaccharide acceptor (XXXII) with imidate (XXXIII) in the presence of tert-butyldimethylsilyl triflate, followed by removal of the levulinate ester with hydrazine acetate, furnishes tetrasaccharide (XXXIV).
【1】 Petitou, M.; Herbert, J.-M.; Duchaussoy, P.; Basten, J.; Dreef-Tromp, C.; Driguez, P.-A.; Van Boeckel, C. (Akzo Nobel N.V.; Sanofi-Synthélabo); Synthetic polysaccharides, their method of production and pharmaceutical compsns. containing same. EP 1049721; FR 2773804; US 6528497; WO 9936443 . |
中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
---|---|---|---|---|---|---|
(XXVII) | 58157 | (4aS,6R,7R,8S,8aS)-6-({(2R,3S,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-8-methoxy-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-yl benzoate | C39H48O12 | 详情 | 详情 | |
(XXVIII) | 58158 | (4aS,6R,7R,8R,8aS)-6-({(2R,3S,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-8-methoxy-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-7-ol | C32H44O11 | 详情 | 详情 | |
(XXIX) | 58159 | (4aS,6R,7R,8R,8aS)-6-({(2R,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-7-methoxy-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-8-yl methyl ether; (4aS,6R,7R,8R,8aS)-6-({(2R,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-7,8-dimethoxy-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxine | C33H46O11 | 详情 | 详情 | |
(XXX) | 58160 | (2S,3S,4S,5R,6S)-6-({(2R,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-2-(hydroxymethyl)-4,5-dimethoxytetrahydro-2H-pyran-3-ol | C30H42O11 | 详情 | 详情 | |
(XXXI) | 58161 | (2R,3S,4S,5R,6R)-6-({(2R,3S,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-3-hydroxy-4,5-dimethoxytetrahydro-2H-pyran-2-carboxylic acid | C30H40O12 | 详情 | 详情 | |
(XXXII) | 58162 | benzyl (2R,3S,4S,5R,6R)-6-({(2R,3S,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-3-hydroxy-4,5-dimethoxytetrahydro-2H-pyran-2-carboxylate | C37H46O12 | 详情 | 详情 | |
(XXXIII) | 58163 | benzyl (2R,3S,4R,5R,6R)-6-({(2R,3R,4R,5R)-4-(acetyloxy)-2-[(acetyloxy)methyl]-5-(benzyloxy)-6-[(2,2,2-trichloroethanimidoyl)oxy]tetrahydro-2H-pyran-3-yl}oxy)-4,5-dimethoxy-3-[(4-oxopentanoyl)oxy]tetrahydro-2H-pyran-2-carboxylate | C39H46Cl3NO16 | 详情 | 详情 | |
(XXXIV) | 58164 | benzyl (2R,3S,4S,5R,6R)-6-{[(2R,3R,4R,5R,6S)-4-(acetyloxy)-2-[(acetyloxy)methyl]-5-(benzyloxy)-6-({(2R,3S,4R,5R,6R)-6-({(2R,3S,4R,5R,6S)-5-(benzyloxy)-2-[(benzyloxy)methyl]-4,6-dimethoxytetrahydro-2H-pyran-3-yl}oxy)-2-[(benzyloxy)carbonyl]-4,5-dimethoxytetrahydro-2H-pyran-3-yl}oxy)tetrahydro-2H-pyran-3-yl]oxy}-3-hydroxy-4,5-dimethoxytetrahydro-2H-pyran-2-carboxylate | C69H84O25 | 详情 | 详情 |