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【结 构 式】 
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【分子编号】69286 【品名】ethyl 1(R)-amino-2(S)-vinylcyclopropanecarboxylate (+)-dibenzoyltartrate 【CA登记号】213316-32-6 |
【 分 子 式 】C8H13NO2 【 分 子 量 】155.19676 【元素组成】C 61.91% H 8.44% N 9.03% O 20.62% |
合成路线1
该中间体在本合成路线中的序号：(XXVII)Condensation of benzaldehyde (XXII) with ethyl glycinate hydrochloride (XXIII) in the presence of Na2SO4 and Et3N in tert-butyl methyl ether gives ethyl[(benzylidene)amino]acetate (XXIV), which upon reaction with 1,4-dibromo-2-butene (XXV) in the presence of t-BuOLi in toluene yields racemic ethyl 1-amino-2-vinylcyclopropanecarboxylate (rac-[XXVI]). Resolution of rac-(XXVI) by treatment with (+)-dibenzoyltartaric acid in EtOAc gives ethyl 1(R)-amino-2(S)-vinylcyclopropanecarboxylate (+)-dibenzoyltartrate (XXVII) salt, which is finally treated with HCl in Et2O .
Alternatively, amino ester (rac-[XXVI]) can be prepared by condensation of ethyl ester (XXVIII) with 1,4-dibromo-2-butene (XXV) in the presence of t-BuOK in THF, followed by treatment of the resulting imine (rac-[XXIX]) with HCl in Et2O and then with NaHCO3 .
| 【1】 Llinas-Brunet, M., Bailey, M.D., Cameron, D. et al. (Boehringer Ingelheim [Canada] Ltd.). Hepatitis C inhibitor tri-peptides. CA 2338946, EP 1105413, EP 2028186, JP 2002522554, US 6323180, WO 2000009543. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| rac-(XXVI) | 69285 | racemic ethyl 1-amino-2-vinylcyclopropanecarboxylate | C8H13NO2 | 详情 | 详情 | |
| rac-(XXIX) | 69287 | racemic ethyl 1-((diphenylmethylene)amino)-2-vinylcyclopropanecarboxylate | C21H21NO2 | 详情 | 详情 | |
| (IX) | 69270 | (1R,2S)-ethyl 1-amino-2-vinylcyclopropanecarboxylate | 746657-36-3 | C8H13NO2 | 详情 | 详情 |
| (XXII) | 10498 | Benzaldehyde;Benzoic aldehyde;Phenylmethanal | 100-52-7 | C7H6O | 详情 | 详情 |
| (XXIII) | 68234 | ethyl glycinate hydrochloride；Glycine ethyl ester hydrochloride | 623-33-6 | C4H9NO2.HCl | 详情 | 详情 |
| (XXIV) | 68235 | (E)-ethyl 2-(benzylideneamino)acetate;2-(benzylideneamino)acetic acid ethyl ester；ethyl N-benzylideneglycinate；Benzylideneglycine ethyl ester；N-Benzylideneglycineethyl ester；ethyl(benzylideneamino)acetate | 40682-54-0 | C11H13NO2 | 详情 | 详情 |
| (XXV) | 18349 | (E)-1,4-dibromo-2-butene；trans-1,4-dibromo-2-butene | 821-06-7 | C4H6Br2 | 详情 | 详情 |
| (XXVII) | 69286 | ethyl 1(R)-amino-2(S)-vinylcyclopropanecarboxylate (+)-dibenzoyltartrate | 213316-32-6 | C8H13NO2 | 详情 | 详情 |
| (XXVIII) | 26772 | ethyl 2-((diphenylmethylene)amino)acetate;N-(Diphenylmethylene)glycine ethyl ester;Ethyl N-(diphenylmethylene)glycinate;ethyl 2-[(dibenzylene)amino]acetate | 69555-14-2 | C17H17NO2 | 详情 | 详情 |