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【结 构 式】 
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【分子编号】62557 【品名】2,2,2-trichloroethyl (2S)-1-{(2S,7S,11S,12R,15S,16R,19S)-15-({(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl}amino)-11-{[tert-butyl(dimethyl)silyl]oxy}-2-isobutyl-7-isopropyl-19-(4-methoxybenzyl)-5,16,20-trimethyl-12-[(1S)-1-methylpro 【CA登记号】 |
【 分 子 式 】C70H109Cl3N6O17Si 【 分 子 量 】1441.1093 【元素组成】C 58.34% H 7.62% Cl 7.38% N 5.83% O 18.87% Si 1.95% |
合成路线1
该中间体在本合成路线中的序号：(LI)Esterification of the peptide alcohol (XLVIII) with the modified tyrosine derivative (II) afforded depsipeptide (XLIX). After reductive cleavage of the trichloroethyl ester of (XLIX), using zinc dust and ammonium acetate, the resultant carboxylic acid (L) was coupled to the alcohol segment (XL) in the presence of DIC and DMAP·CF3COOH to furnish the linear precursor depsipeptide (LI)
| 【1】 Jou, G.; Gonzalez, I.; Albericio, F.; Lloyd-Williams, P.; Giralt, E.; Total synthesis of dehydrodidemnin B. Use of uronium and phosphonium salt coupling reagents in peptide synthesis in solution. J Org Chem 1997, 62, 2, 354. |
| 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) | 50747 | (2S)-2-[[(benzyloxy)carbonyl](methyl)amino]-3-(4-methoxyphenyl)propionic acid | C19H21NO5 | 详情 | 详情 | |
| (XL) | 62549 | 2,2,2-trichloroethyl (2S)-1-((2S)-2-{[(4S)-4-hydroxy-2,5-dimethyl-3-oxohexanoyl]amino}-4-methylpentanoyl)-2-pyrrolidinecarboxylate | C21H33Cl3N2O6 | 详情 | 详情 | |
| (XLVIII) | 50784 | 2,2,2-trichloroethyl (6R,9S,12R,13S)-13-[[tert-butyl(dimethyl)silyl]oxy]-9-[(1R)-1-hydroxyethyl]-6-isobutyl-2,2,5-trimethyl-12-[(1S)-1-methylpropyl]-4,7,10-trioxo-3-oxa-5,8,11-triazapentadecan-15-oate | C32H60Cl3N3O8Si | 详情 | 详情 | |
| (XLIX) | 62555 | 2,2,2-trichloroethyl (5S,8R,9S,12R,13S)-9-({(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl}amino)-13-{[tert-butyl(dimethyl)silyl]oxy}-5-(4-methoxybenzyl)-4,8-dimethyl-12-[(1S)-1-methylpropyl]-3,6,10-trioxo-1-phenyl-2,7-dioxa-4,11-diaz | C51H79Cl3N4O12Si | 详情 | 详情 | |
| (L) | 62556 | (5S,8R,9S,12R,13S)-9-({(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl}amino)-13-{[tert-butyl(dimethyl)silyl]oxy}-5-(4-methoxybenzyl)-4,8-dimethyl-12-[(1S)-1-methylpropyl]-3,6,10-trioxo-1-phenyl-2,7-dioxa-4,11-diazapentadecan-15-oic ac | C49H78N4O12Si | 详情 | 详情 | |
| (LI) | 62557 | 2,2,2-trichloroethyl (2S)-1-{(2S,7S,11S,12R,15S,16R,19S)-15-({(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl}amino)-11-{[tert-butyl(dimethyl)silyl]oxy}-2-isobutyl-7-isopropyl-19-(4-methoxybenzyl)-5,16,20-trimethyl-12-[(1S)-1-methylpro | C70H109Cl3N6O17Si | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(LI)Sequential deprotection of the trichloroethyl ester and the N-benzyloxycarbonyl groups of (LI) led to (LII) and the linear aminoacid (LIII), which underwent macrocyclization to the N-Boc didemnin A (XXVIII) upon treatment with HATU and HOAt. The title compound was then obtained by acidic Boc group deprotection, followed by coupling with pyruvyl proline as outlined in Schemes 23437701e and 23437701f
| 【1】 Jou, G.; Gonzalez, I.; Albericio, F.; Lloyd-Williams, P.; Giralt, E.; Total synthesis of dehydrodidemnin B. Use of uronium and phosphonium salt coupling reagents in peptide synthesis in solution. J Org Chem 1997, 62, 2, 354. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXVIII) | 62560 | C60H100N6O14Si | 详情 | 详情 | ||
| (LI) | 62557 | 2,2,2-trichloroethyl (2S)-1-{(2S,7S,11S,12R,15S,16R,19S)-15-({(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl}amino)-11-{[tert-butyl(dimethyl)silyl]oxy}-2-isobutyl-7-isopropyl-19-(4-methoxybenzyl)-5,16,20-trimethyl-12-[(1S)-1-methylpro | C70H109Cl3N6O17Si | 详情 | 详情 | |
| (LII) | 62558 | (2S)-1-{(2S,7S,11S,12R,15S,16R,19S)-15-({(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl}amino)-11-{[tert-butyl(dimethyl)silyl]oxy}-2-isobutyl-7-isopropyl-19-(4-methoxybenzyl)-5,16,20-trimethyl-12-[(1S)-1-methylpropyl]-4,6,9,14,18,21-h | C68H108N6O17Si | 详情 | 详情 | |
| (LIII) | 62559 | (2S)-1-{(2S,7S,11S,12R,15S,18R)-11-{[tert-butyl(dimethyl)silyl]oxy}-2,18-diisobutyl-7-isopropyl-15-((1R)-1-{[(2S)-3-(4-methoxyphenyl)-2-(methylamino)propanoyl]oxy}ethyl)-5,19,22,22-tetramethyl-12-[(1S)-1-methylpropyl]-4,6,9,14,17,20-hexaoxo-8,21-dio | C60H102N6O15Si | 详情 | 详情 |