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【结 构 式】 
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【分子编号】11147 【品名】di(tert-butyl) carbonate 【CA登记号】 |
【 分 子 式 】C9H18O3 【 分 子 量 】174.24012 【元素组成】C 62.04% H 10.41% O 27.55% |
合成路线1
该中间体在本合成路线中的序号：(II)A-21978C nucleus (I) (obtained by deacylating A-21978C complex by fermentation with Actinoplanes utahensis NRRL 12052) is protected with di-tert-butyl carbonate (II) and NaOH in water to give the N-(Orn-)-tert-butoxycarbonyl derivative (III), which is treated with 2,4,5-trichlorophenyl decanoate (IV) in hot DMF yielding the protected decanoyl derivative (V). Finally, this compound is deprotected with trifluoroacetic acid / 1,2-ethanedithiol.
| 【1】 Abbott, B.J.; Debono, M.; Fukuda, D.S. (Eli Lilly and Company); Derivs. of A-21978C cyclic peptides. US 4537717 . |
| 【2】 Dionisi, M.S.; Patoia, L.; Castaner, J.; Daptomycin. Drugs Fut 1991, 16, 7, 608. |
合成路线2
该中间体在本合成路线中的序号：(II)Synthesis of intermediate (VI): Treatment of 2-oxopiperazine (I) with di-t-butyl dicarbonate (II) and Et3N in DMF affords 1-t-butoxycarbonyl-3-oxopiperazine (III), which is then condensed with bromo derivative (IV) by means of NaH in THF, providing ethyl phenoxyacetate derivative (V). Treatment of (V) with HCl/EtOAc allows removal of the t-butyloxycarbonyl group, yielding intermediate (VI). Alternatively, intermediate (VI) can be obtained by first formylation of (I) with formic acid and acetic anhydride (Ac2O) in CH2Cl2 to afford derivative (VII), followed by condensation of (VII) with (IV) to give (VIII) by means of NaH in DMF/THF and deformylation by treatment with HCl/EtOAc to afford (VI).
| 【1】 Ohuchi, S.; Suzuki, H.; Ando, T.; Katano, K.; Imai, T.; Kobayashi, K.; Ota, K.; Aizawa, K.; Miura, T. (Meiji Seika Kaisha, Ltd.); Nitrogen-containing heterocyclic cpds. having antiplatelet aggregation effect and medicinal use thereof. EP 1070712; WO 9952894 . |
| 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) | 44876 | 2-piperazinone | C4H8N2O | 详情 | 详情 | |
| (II) | 11147 | di(tert-butyl) carbonate | C9H18O3 | 详情 | 详情 | |
| (III) | 44877 | tert-butyl 3-oxo-1-piperazinecarboxylate | C9H16N2O3 | 详情 | 详情 | |
| (IV) | 44878 | ethyl 2-[4-(1lambda(3)-dibromanylcarbonyl)phenoxy]acetate | C11H12Br2O4 | 详情 | 详情 | |
| (V) | 44879 | tert-butyl 4-[2-[4-(2-ethoxy-2-oxoethoxy)phenyl]-2-oxoethyl]-3-oxo-1-piperazinecarboxylate | C21H28N2O7 | 详情 | 详情 | |
| (VI) | 44880 | ethyl 2-[4-[2-(2-oxo-1-piperazinyl)acetyl]phenoxy]acetate | C16H20N2O5 | 详情 | 详情 | |
| (VII) | 44881 | 3-oxo-1-piperazinecarbaldehyde | C5H8N2O2 | 详情 | 详情 | |
| (VIII) | 44882 | ethyl 2-[4-[2-(4-formyl-2-oxo-1-piperazinyl)acetyl]phenoxy]acetate | C17H20N2O6 | 详情 | 详情 |