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【结 构 式】 
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【分子编号】38660 【品名】(1R,2S,3R,4R,5R)-2-(benzyloxy)-4-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octan-3-ol 【CA登记号】 |
【 分 子 式 】C14H18O5 【 分 子 量 】266.29392 【元素组成】C 63.15% H 6.81% O 30.04% |
合成路线1
该中间体在本合成路线中的序号：(III)The reaction of 1,6:2,3-dianhydro-4-O-benzyl-beta-D-mannopyranose (I) with vinylmagnesium bromide in THF gives 1,6-anhydro-4-O-benzyl-2-deoxy-2-C-vinyl-beta-D-glucopyranose (II), which is treated with O3 and NaBH4 in EtOH/H2O yielding 1,6-anhydro-4-O-benzyl-2-deoxy-2-C-(hydroxymethyl)-beta-D-glucopyranose (III). The hydrolysis of (III) with aqueous refluxing H2SO4 affords 4-O-benzyl-2-deoxy-2-C-(hydroxymethyl)-D-glucopyranose (IV), which is oxidized with NaIO4 in MeOH giving 4-O-benzyl-2-deoxy-2-C-(hydroxymethyl)-D-xylo-pentodialdose (V). The reductocyclization of (V) with ammonia and H2 over Pd/C provides the benzylated target compound (VI), which is finally deprotected with H2 over Pd/C in EtOH/HCl furnishing the target compound as a single (R,R,R) enantiomer.
| 【1】 Lundgren, K.; Kirk, O. (Novo Nordisk A/S); Piperidines and pyrrolidines. EP 0749423; JP 1997509947; WO 9524391 . |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 16524 | bromo(vinyl)magnesium | 1826-67-1 | C2H3BrMg | 详情 | 详情 | |
| (I) | 38658 | (1R,2S,4R,5S,6R)-5-(benzyloxy)-3,8,9-trioxatricyclo[4.2.1.0(2,4)]nonane; benzyl (1R,2S,4R,5S,6R)-3,8,9-trioxatricyclo[4.2.1.0(2,4)]non-5-yl ether | 33208-47-8 | C13H14O4 | 详情 | 详情 |
| (II) | 38659 | (1R,2S,3R,4R,5R)-2-(benzyloxy)-4-vinyl-6,8-dioxabicyclo[3.2.1]octan-3-ol | C15H18O4 | 详情 | 详情 | |
| (III) | 38660 | (1R,2S,3R,4R,5R)-2-(benzyloxy)-4-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octan-3-ol | C14H18O5 | 详情 | 详情 | |
| (IV) | 38661 | (3R,4R,5S,6R)-5-(benzyloxy)-3,6-bis(hydroxymethyl)tetrahydro-2H-pyran-2,4-diol | C14H20O6 | 详情 | 详情 | |
| (V) | 38662 | (2S,3R,4R)-2-(benzyloxy)-3-hydroxy-4-(hydroxymethyl)pentanedial | C13H16O5 | 详情 | 详情 | |
| (VI) | 38663 | (3R,4R,5R)-3-(benzyloxy)-5-(hydroxymethyl)-4-piperidinol | C13H19NO3 | 详情 | 详情 |