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【结 构 式】 
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【分子编号】61574 【品名】[(3aR,5R,6aS)-2,2-dimethyl-6-oxotetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl 4-chlorobenzoate 【CA登记号】 |
【 分 子 式 】C15H15ClO6 【 分 子 量 】326.7332 【元素组成】C 55.14% H 4.63% Cl 10.85% O 29.38% |
合成路线1
该中间体在本合成路线中的序号：(IV)The reaction of 1,2-O-isopropylidene-D-xylofuranose (I) with 4-chlorobenzoyl chloride (II) and TEA gives the 5-O-(4-chlorobenzoate) (III), which is oxidized with TEMPO and NaClO to yield the 3-oxo derivative (IV). The ethynylation of (IV) by means of trimethylsilylethynyl magnesium bromide (V) affords the 3-C-trimethylsilylethynyl derivative (VI), which is hydrolyzed by means of refluxing aqueous HCOOH to provide the 3-C-ethynylated sugar (VII). The acylation of (VII) by means of 4-chlorobenzoyl chloride (II), TEA and DMAP gives the tetrabenzoate sugar (VIII), which is used for the glycosylation of bis trimethylsilyl cytosine (IX) by means of SnCl4 to yield the protected precursor (X). Finally, this compound is desilylated and debenzoylated by means of DBU in hot methanol to afford the target nucleoside.
| 【1】 Nomura, M.; Sato, T.; Masato, W.; Tanaka, M.; Asao, T.; Shuto, S.; Matsuda, A.; Nucleosides and nucleotides. Part 212: Practical large-scale synthesis of 1-(3-C-ethynyl-beta-D-ribo-pentofuranosyl)cytosine (ECyd), a potent antitumor nucleoside. Isobutyryloxy group as an efficient anomeric leaving group in the Vorbruggen glycosylation . Tetrahedron 2002, 58, 7, 1279. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 41907 | (3aR,5R,6S,6aR)-5-(hydroxymethyl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-ol | 20031-21-4 | C8H14O5 | 详情 | 详情 |
| (II) | 10295 | p-Chlorobenzoyl chloride; 4-Chlorobenzoyl chloride | 122-01-0 | C7H4Cl2O | 详情 | 详情 |
| (III) | 61573 | [(3aR,5R,6S,6aR)-6-hydroxy-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl 4-chlorobenzoate | C15H17ClO6 | 详情 | 详情 | |
| (IV) | 61574 | [(3aR,5R,6aS)-2,2-dimethyl-6-oxotetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl 4-chlorobenzoate | C15H15ClO6 | 详情 | 详情 | |
| (V) | 34561 | methyl 3-methyl-1-(2-methylphenyl)-2-(trimethylsilyl)-1H-pyrrolo[3,2-c]quinolin-6-yl ether; 6-methoxy-3-methyl-1-(2-methylphenyl)-2-(trimethylsilyl)-1H-pyrrolo[3,2-c]quinoline | C23H26N2OSi | 详情 | 详情 | |
| (VI) | 61575 | {(3aR,5R,6R,6aR)-6-hydroxy-2,2-dimethyl-6-[2-(trimethylsilyl)ethynyl]tetrahydrofuro[2,3-d][1,3]dioxol-5-yl}methyl 4-chlorobenzoate | C20H25ClO6Si | 详情 | 详情 | |
| (VII) | 61576 | {(2R,3S,4R)-3,4,5-trihydroxy-3-[2-(trimethylsilyl)ethynyl]tetrahydro-2-furanyl}methyl 4-chlorobenzoate | C17H21ClO6Si | 详情 | 详情 | |
| (VIII) | 61577 | (3R,4R,5R)-3,4-bis[(4-chlorobenzoyl)oxy]-5-{[(4-chlorobenzoyl)oxy]methyl}-4-[2-(trimethylsilyl)ethynyl]tetrahydro-2-furanyl 4-chlorobenzoate | C38H30Cl4O9Si | 详情 | 详情 | |
| (IX) | 61578 | N-(trimethylsilyl)-2-[(trimethylsilyl)oxy]-4-pyrimidinamine; N-(trimethylsilyl)-N-{2-[(trimethylsilyl)oxy]-4-pyrimidinyl}amine | C10H21N3OSi2 | 详情 | 详情 | |
| (X) | 61579 | (2R,3R,4R,5R)-4-[(4-chlorobenzoyl)oxy]-5-{[(4-chlorobenzoyl)oxy]methyl}-2-[2-oxo-4-[(trimethylsilyl)amino]-1(2H)-pyrimidinyl]-4-[2-(trimethylsilyl)ethynyl]tetrahydro-3-furanyl 4-chlorobenzoate | C38H38Cl3N3O8Si2 | 详情 | 详情 |