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【结 构 式】 
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【分子编号】12238 【品名】5-Methyl-1,3-bis(trimethylsilyl)-2,4(1H,3H)-pyrimidinedione 【CA登记号】3444-09-5 |
【 分 子 式 】C11H22N2O2Si2 【 分 子 量 】270.47896 【元素组成】C 48.85% H 8.2% N 10.36% O 11.83% Si 20.77% |
合成路线1
该中间体在本合成路线中的序号：(V)A new asymmetric synthesis of stavudine has been described: The regioselective epoxidation of allyl alcohol (I) by means of titanium tetraisopropoxide and alpha,alpha-dimethylbenzylperoxide, catalyzed by diisopropyl D-tartrate, followed by esterification with pivaloyl chloride yields the epoxide (II), which is then condensed with lithium acetylide catalyzed by boron trifluoride ethearate in THF, yielding the acetylenic alcohol (III). The cyclization of (III) catalyzed by Mo(CO)6 and trimethylamine oxide affords the dihydrofuran (IV), which is condensed with N,N'-bis(trimethylsilyl)thymine (V) and I2 to give the iodonucleoside (VI). Finally, this compound is dehydroiodinated and deprotected with sodium methoxide in methanol.
| 【1】 Gleason, M.M.; McDonald, F.E.; Asymmetric syntheses of stavudine (d4T) and cordycepin by cycloisomerization of alkynyl alcohols to endocyclic enol ethers. Angew Chem. Int Ed Engl 1995, 34, 3, 350. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 17461 | ethynyllithium | C2HLi | 详情 | 详情 | ||
| (I) | 12234 | 2-Propen-1-ol; Allyl alcohol | 107-18-6 | C3H6O | 详情 | 详情 |
| (II) | 12235 | (2S)oxiranylmethyl pivalate | C8H14O3 | 详情 | 详情 | |
| (III) | 12236 | (2S)-2-hydroxy-4-pentynyl pivalate | C10H16O3 | 详情 | 详情 | |
| (IV) | 12226 | (2S)-2,3-dihydro-2-furanylmethyl pivalate | C10H16O3 | 详情 | 详情 | |
| (V) | 12238 | 5-Methyl-1,3-bis(trimethylsilyl)-2,4(1H,3H)-pyrimidinedione | 3444-09-5 | C11H22N2O2Si2 | 详情 | 详情 |
| (VI) | 12239 | [(2S,4R,5R)-4-iodo-5-[5-methyl-2,4-dioxo-3,4-dihydro-1(2H)-pyrimidinyl]tetrahydro-2-furanyl]methyl pivalate | C15H21IN2O5 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(XI)
| 【1】 Storer R. Moussa A. Wang JY. et al. 2005. Synthesis of β-L-2-deoxy-nucleosides from furanoses and pyranoses via a chloro-sugar and anhydro-l-furanosyl-nucleobase intennediatcs as potential antiviral and antineoplastic agents. W0 2005003374 |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (II) | 66768 | (3S,5S)-3,4-dihydroxy-5-(hydroxymethyl)dihydrofuran-2(3H)-one | C5H8O5 | 详情 | 详情 | |
| (VI) | 66772 | 4-hydroxy-5-(hydroxymethyl)dihydrofuran-2(3H)-one | C5H8O4 | 详情 | 详情 | |
| （X） | 12204 | 5-Methyl-2,4(1H,3H)-pyrimidinedione; Thymine | 65-71-4 | C5H6N2O2 | 详情 | 详情 |
| (I) | 66767 | (3S,4R,5S)tetrahydro-2H-pyran-2,3,4,5-tetrol | C5H10O5 | 详情 | 详情 | |
| (III) | 66769 | 3-bromo-5-(bromomethyl)-4-hydroxydihydrofuran-2(3H)-one | C5H6Br2O3 | 详情 | 详情 | |
| (IV) | 66770 | 5-(bromomethyl)-4-hydroxydihydrofuran-2(3H)-one | C5H7BrO3 | 详情 | 详情 | |
| (V) | 66771 | potassium 3-hydroxy-3-(oxiran-2-yl)propanoate | C5H7KO4 | 详情 | 详情 | |
| (VII) | 66773 | C21H21O6 | 详情 | 详情 | ||
| (VIII) | 62916 | {(2S,3R)-5-hydroxy-3-[(4-methylbenzoyl)oxy]tetrahydro-2-furanyl}methyl 4-methylbenzoate | C21H22O6 | 详情 | 详情 | |
| (IX) | 37194 | (2R,3S)-5-Chloro-2-[[(4-methylbenzoyl)oxy]methyl]tetrahydro-3-furanyl 4-methylbenzoate | 4330-21-6 | C21H21ClO5 | 详情 | 详情 |
| (XI) | 12238 | 5-Methyl-1,3-bis(trimethylsilyl)-2,4(1H,3H)-pyrimidinedione | 3444-09-5 | C11H22N2O2Si2 | 详情 | 详情 |
| (XII) | 62918 | {(2S,3R,5S)-3-[(4-methylbenzoyl)oxy]-5-[5-methyl-2,4-dioxo-3,4-dihydro-1(2H)-pyrimidinyl]tetrahydro-2-furanyl}methyl 4-methylbenzoate | C26H26N2O7 | 详情 | 详情 |