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【结 构 式】 
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【分子编号】40563 【品名】methyl (8R,11R,14S,15R)-11-(3-bromo-4-methylphenyl)-8-[(tert-butoxycarbonyl)amino]-15-[[tert-butyl(dimethyl)silyl]oxy]-4,5-dihydroxy-18-nitro-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.2.2.1(3,7)]henicosa-1(18),3(21),4,6,16,19-hexaene-14-carboxylate 【CA登记号】 |
【 分 子 式 】C39H49BrN4O12Si 【 分 子 量 】873.82732 【元素组成】C 53.61% H 5.65% Br 9.14% N 6.41% O 21.97% Si 3.21% |
合成路线1
该中间体在本合成路线中的序号：(XIII)The cyclization of tripeptide derivative (XII) (assembled n three steps from the corresponding amino acids) by means of K2CO3/CaCO3 gives the macrocyclic peptide (XIII), which was reduced at its NO2 group with H2 over Pd/C and treated with tert-butyl nitrite, HBF4 and CuCl2 to obtain the corresponding chloro derivative (XIV). The condensation of (XIV) with the boronic acid derivative (XV) by means of a Pd catalyst affords the biphenyl derivative (XVI), which is desilylated with Bu4NF giving the secondary alcohol (XVII). The hydrolysis of the methyl ester of (XVII) with LiOH yields the corresponding carboxylic acid (XVIII).
| 【1】 Boger, D.L.; et al.; First and second generation total synthesis of the teicoplanin aglycon. J Am Chem Soc 2001, 123, 9, 1862. |
| 【2】 Boger, D.L.; et al.; Total synthesis of the vancomycin aglycon. J Am Chem Soc 1999, 121, 43, 10004. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XII) | 40562 | methyl (6R,9R)-9-(3-bromo-4-methylphenyl)-12-[(R)-[[tert-butyl(dimethyl)silyl]oxy](4-fluoro-3-nitrophenyl)methyl]-6-(3,5-dihydroxy-4-methylphenyl)-2,2-dimethyl-4,7,10-trioxo-3-oxa-5,8,11-triazatridecan-13-oate | C39H50BrFN4O12Si | 详情 | 详情 | |
| (XIII) | 40563 | methyl (8R,11R,14S,15R)-11-(3-bromo-4-methylphenyl)-8-[(tert-butoxycarbonyl)amino]-15-[[tert-butyl(dimethyl)silyl]oxy]-4,5-dihydroxy-18-nitro-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.2.2.1(3,7)]henicosa-1(18),3(21),4,6,16,19-hexaene-14-carboxylate | C39H49BrN4O12Si | 详情 | 详情 | |
| (XIV) | 40564 | methyl (8R,11R,14S,15R)-11-(3-bromo-4-methylphenyl)-8-[(tert-butoxycarbonyl)amino]-15-[[tert-butyl(dimethyl)silyl]oxy]-18-chloro-4,5-dihydroxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.2.2.1(3,7)]henicosa-1(18),3(21),4,6,16,19-hexaene-14-carboxylate | C39H49BrClN3O10Si | 详情 | 详情 | |
| (XV) | 40565 | 2-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4,6-dimethylphenylboronic acid | C22H30BNO7 | 详情 | 详情 | |
| (XVI) | 40566 | methyl (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-15-[[tert-butyl(dimethyl)silyl]oxy]-18-chloro-5-hydroxy-4-methoxy-9,12-diox; methyl (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-15-[[tert-butyl(dimethyl)silyl]oxy]-18-chloro-5-hydroxy-4-methoxy-9,12-diox; methyl (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-15-[[tert-butyl(dimethyl)silyl]oxy]-18-chloro-5-hydroxy-4-methoxy-9,12-diox | C61H77ClN4O18Si | 详情 | 详情 | |
| (XVII) | 40567 | methyl (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-18-chloro-5,15-dihydroxy-4-methoxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.; methyl (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-18-chloro-5,15-dihydroxy-4-methoxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.; methyl (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-18-chloro-5,15-dihydroxy-4-methoxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14. | C55H63ClN4O18 | 详情 | 详情 | |
| (XVIII) | 40568 | (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-18-chloro-5,15-dihydroxy-4-methoxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.2.2.1(3; (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-18-chloro-5,15-dihydroxy-4-methoxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.2.2.1(3; (8R,11R,14S,15R)-11-(2'-[(1S)-1-[[(benzyloxy)carbonyl]amino]-2-[(2-methoxyethoxy)methoxy]ethyl]-4',6,6'-trimethoxy[1,1'-biphenyl]-3-yl)-8-[(tert-butoxycarbonyl)amino]-18-chloro-5,15-dihydroxy-4-methoxy-9,12-dioxo-2-oxa-10,13-diazatricyclo[14.2.2.1(3 | C54H61ClN4O18 | 详情 | 详情 |