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【结 构 式】 
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【分子编号】66005 【品名】methyl (3aS,4R,7aR)-4-[(1R,2R)-1,2,3-trihydroxy-propyl]-2-methyl-3a,7a-dihydro-4H-pyrano[3,4-d][1,3]oxazole-6-carboxylate 【CA登记号】1072449-83-2 |
【 分 子 式 】C12H17NO7 【 分 子 量 】287.26952 【元素组成】C 50.17% H 5.96% N 4.88% O 38.99% |
合成路线1
该中间体在本合成路线中的序号：(XVIII)The synthetic precursor (X) is prepared by esterification of N-acetyl-2,3-didehydroneuraminic acid (XV) with MeOH in the presence of HC(OMe)3 and H2SO4 at 40 °C to yield the methyl ester (XVI), which by O-acylation with AcOH by means of H2SO4 in heptane at 40 °C followed by cyclization in the presence of NH3 and Et3N in toluene/H2O furnishes the pyrano[3,4-d]oxazole derivative (XVII). Hydrolysis of the triacetate (XVII) by means of NaOMe in MeOH gives the corresponding triol (XVIII), which is protected again at the vicinal 8,9-hydroxyl groups as the cyclic carbonate (XIX) by means of CO(OMe)2 in MeOH. Then, methylation of the free C-7 hydroxyl group with Me2SO4 in the presence of NaH in THF/DMA gives the corresponding methyl ether (XX), which is submitted to oxazoline ring opening with Me3SiN3 in the presence of (i-PrO)4Ti in t-BuOH to furnish the acetamido azide (XXI). Finally, azide (XXI) is reduced by means of PPh3 in THF or EtOAc (3). Scheme 2.
| 【3】 Nakamura, Y., Murakami, M., Yamaoka, M., Wakayama, M., Umeo, K. (Daiichi Sankyo Co., Ltd.). Method for manufacturing neuraminic acid derivatives. EP 2132191, JP 2010523472, WO 2008126943. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (X) | 65998 | C14H20N2O8 | 详情 | 详情 | ||
| (XV) | 66002 | N-Acetyl-2,3-dehydro-2-deoxyneuraminic acid; 2-Deoxy-2,3-Didehydro-D-N--Acetylneuraminic Acid | 24967-27-9 | C11H17NO8 | 详情 | 详情 |
| (XVI) | 66003 | methyl (2R,3R,4S)-3-acetamido-4-hydroxy-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylate | 25875-99-4 | C12H19NO8 | 详情 | 详情 |
| (XVII) | 66004 | Methyl (3aR,4R,7aR)-2-methyl-4-[(1S,2R)-1,2,3-triacetoxypropyl]-3a,7a-dihydro-4H-pyrano[3,4-d][1,3]oxazole-6-carboxylate | 78850-37-0 | C18H23NO10 | 详情 | 详情 |
| (XVIII) | 66005 | methyl (3aS,4R,7aR)-4-[(1R,2R)-1,2,3-trihydroxy-propyl]-2-methyl-3a,7a-dihydro-4H-pyrano[3,4-d][1,3]oxazole-6-carboxylate | 1072449-83-2 | C12H17NO7 | 详情 | 详情 |
| (XIX) | 66006 | C13H15NO8 | 详情 | 详情 | ||
| (XX) | 66007 | C14H17NO8 | 详情 | 详情 | ||
| (XXI) | 66008 | C14H18N4O8 | 详情 | 详情 |