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【结 构 式】 
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【分子编号】50764 【品名】(1S,2S,3R)-4-hydroxy-1-isopropyl-2-(methoxymethoxy)-3-methylbutyl (3S,4R,5S)-4-([(2S,3R)-3-[[(2S)-2-[[[(2S)-1-((2S)-2-[[(benzyloxy)carbonyl]amino]-4-methylpentanoyl)pyrrolidinyl]carbonyl](methyl)amino]-3-(4-methoxyphenyl)propanoyl]oxy]-2-[(tert-butoxycarbonyl)amino]butanoyl]amino)-5-methyl-3-[(triisopropylsilyl)oxy]heptanoate 【CA登记号】 |
【 分 子 式 】C66H109N5O16Si 【 分 子 量 】1256.70106 【元素组成】C 63.08% H 8.74% N 5.57% O 20.37% Si 2.23% |
合成路线1
该中间体在本合成路线中的序号：(XXV)Removal of the tert-butyldimethylsilyl group of (XXIV) by means of HOAc/THF/H2O yields alcohol (XXV), which is then converted into carboxylic acid (XXVI) by first Swern oxidation with trifluoroacetic anhydride, Et3N and DMSO, followed by reaction with KMnO4 in tert-butyl alcohol with sodium hydrogen phosphate. Cyclization of linear peptide (XXVI) is then performed by first removal of the Z protecting group by hydrogenation over Pd/C in MeOH/AcOEt, followed by treatment of the amine with diphenylphosphoryl azide (DPPA) and NaHCO3 in DMF, yielding protected macrolide (XXVII). Removal of the MOM protecting group of (XXVII) by means of dimethylboron bromide in CH2Cl2 affords compound (XXVIII), which is converted into intermediate (XXIX) by Swern oxidation with trifluoroacetic anhydride, Et3N and DMSO, followed by Boc removal with HCl.
| 【1】 Li, W.-R.; et al.; Total synthesis and structural investigations of didemnins A, B, and C. J Am Chem Soc 1990, 112, 21, 7659. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XXIV) | 50763 | (1S,2S,3R)-4-[[tert-butyl(dimethyl)silyl]oxy]-1-isopropyl-2-(methoxymethoxy)-3-methylbutyl (3S,4R,5S)-4-([(2S,3R)-3-[[(2S)-2-[[[(2S)-1-((2S)-2-[[(benzyloxy)carbonyl]amino]-4-methylpentanoyl)pyrrolidinyl]carbonyl](methyl)amino]-3-(4-methoxyphenyl)propanoyl]oxy]-2-[(tert-butoxycarbonyl)amino]butanoyl]amino)-5-methyl-3-[(triisopropylsilyl)oxy]heptanoate | C72H123N5O16Si2 | 详情 | 详情 | |
| (XXV) | 50764 | (1S,2S,3R)-4-hydroxy-1-isopropyl-2-(methoxymethoxy)-3-methylbutyl (3S,4R,5S)-4-([(2S,3R)-3-[[(2S)-2-[[[(2S)-1-((2S)-2-[[(benzyloxy)carbonyl]amino]-4-methylpentanoyl)pyrrolidinyl]carbonyl](methyl)amino]-3-(4-methoxyphenyl)propanoyl]oxy]-2-[(tert-butoxycarbonyl)amino]butanoyl]amino)-5-methyl-3-[(triisopropylsilyl)oxy]heptanoate | C66H109N5O16Si | 详情 | 详情 | |
| (XXVI) | 50765 | (3S,6R,7S,10R,11S,15S,16S,17S)-1-[(2S)-1-((2S)-2-[[(benzyloxy)carbonyl]amino]-4-methylpentanoyl)pyrrolidinyl]-7-[(tert-butoxycarbonyl)amino]-15-isopropyl-3-(4-methoxybenzyl)-16-(methoxymethoxy)-2,6,17-trimethyl-10-[(1S)-1-methylpropyl]-1,4,8,13-tetraoxo-11-[(triisopropylsilyl)oxy]-5,14-dioxa-2,9-diazaoctadecan-18-oic acid | C66H107N5O17Si | 详情 | 详情 | |
| (XXVII) | 50766 | tert-butyl (3S,6R,7S,10R,11S,15S,16S,17S,20S,25aS)-20-isobutyl-15-isopropyl-3-(4-methoxybenzyl)-16-(methoxymethoxy)-2,6,17-trimethyl-10-[(1S)-1-methylpropyl]-1,4,8,13,18,21-hexaoxo-11-[(triisopropylsilyl)oxy]docosahydro-15H-pyrrolo[2,1-f][1,15,4,7,10,20]dioxatetraazacyclotricosin-7-ylcarbamate | C58H99N5O14Si | 详情 | 详情 | |
| (XXVIII) | 50767 | tert-butyl (3S,6R,7S,10R,11S,15S,16S,17S,20S,25aS)-16-hydroxy-20-isobutyl-15-isopropyl-3-(4-methoxybenzyl)-2,6,17-trimethyl-10-[(1S)-1-methylpropyl]-1,4,8,13,18,21-hexaoxo-11-[(triisopropylsilyl)oxy]docosahydro-15H-pyrrolo[2,1-f][1,15,4,7,10,20]dioxatetraazacyclotricosin-7-ylcarbamate | C56H95N5O13Si | 详情 | 详情 | |
| (XXIX) | 50768 | (3S,6R,7S,10R,11S,15S,17S,20S,25aS)-7-amino-11-hydroxy-20-isobutyl-15-isopropyl-3-(4-methoxybenzyl)-2,6,17-trimethyl-10-[(1S)-1-methylpropyl]tetradecahydro-15H-pyrrolo[2,1-f][1,15,4,7,10,20]dioxatetraazacyclotricosine-1,4,8,13,16,18,21(17H)-heptone | C42H65N5O11 | 详情 | 详情 |