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【结 构 式】 
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【分子编号】40318 【品名】methyl (1R,8S,11R,12R,13R)-8-[2-(tert-butoxy)-2-oxoethyl]-12-[[(4S,5S)-5-butyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]-11-[(E)-6-octenyl]-3,5-dioxo-13-(propylsulfanyl)-4-oxatricyclo[7.3.1.0(2,6)]trideca-2(6),9-diene-8-carboxylate 【CA登记号】 |
【 分 子 式 】C41H62O9S 【 分 子 量 】731.00388 【元素组成】C 67.37% H 8.55% O 19.7% S 4.39% |
合成路线1
该中间体在本合成路线中的序号：(XVII)The successive treatment of (XV) with LiOH and Ba(OH)2 caused selective hydrolyses of the thiomaleic group and the less hindered methyl ester, yielding finally monocarboxylic acid (XVI). The conventional Arndt-Eister (oxalyl chloride, diazomethane and silver benzoate/tert-butanol) was used to convert acid (XVI) into the homologated ester (XVII). Careful oxidation of the sulfanyl group of (XVII) with MCPBA followed by a treatment with trifluoroacetic anhydride yields the ketone (XVIII), which is hydrolyzed and cyclized by means of 80% AcOH affording the cyclic acetal (XIX). Finally, this compound is oxidized with Jones reagent and the tert-butyl ester is deprotected with formic acid to provide the target compound.
| 【1】 Waizumi, N.; et al.; Total synthesis of (-)-CP-263,114 (phomoidride B). J Am Chem Soc 2000, 122, 32, 7825. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (XV) | 40316 | dimethyl (1R,11R,12R,13R)-12-[[(4S,5S)-5-butyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]-11-[(E)-6-octenyl]-3,5-dioxo-13-(propylsulfanyl)-4-thiatricyclo[7.3.1.0(2,6)]trideca-2(6),9-diene-8,8-dicarboxylate | C37H54O8S2 | 详情 | 详情 | |
| (XVI) | 40317 | (1R,8R,11R,12R,13R)-12-[[(4S,5S)-5-butyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]-8-(methoxycarbonyl)-11-[(E)-6-octenyl]-3,5-dioxo-13-(propylsulfanyl)-4-oxatricyclo[7.3.1.0(2,6)]trideca-2(6),9-diene-8-carboxylic acid | C36H52O9S | 详情 | 详情 | |
| (XVII) | 40318 | methyl (1R,8S,11R,12R,13R)-8-[2-(tert-butoxy)-2-oxoethyl]-12-[[(4S,5S)-5-butyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]-11-[(E)-6-octenyl]-3,5-dioxo-13-(propylsulfanyl)-4-oxatricyclo[7.3.1.0(2,6)]trideca-2(6),9-diene-8-carboxylate | C41H62O9S | 详情 | 详情 | |
| (XVIII) | 40319 | methyl (1R,8S,11R,12R)-8-[2-(tert-butoxy)-2-oxoethyl]-12-[[(4S,5S)-5-butyl-2,2-dimethyl-1,3-dioxolan-4-yl]methyl]-11-[(E)-6-octenyl]-3,5,13-trioxo-4-oxatricyclo[7.3.1.0(2,6)]trideca-2(6),9-diene-8-carboxylate | C38H54O10 | 详情 | 详情 | |
| (XIX) | 40320 | tert-butyl 2-[(2R,12R,13S,14R,15S)-14-butyl-15-(hydroxymethyl)-12-[(E)-6-octenyl]-4,6,18-trioxo-5,16,17-trioxapentacyclo[7.7.2.0(1,10).0(2,13).0(3,7)]octadeca-3(7),10-dien-9-yl]acetate | C34H46O9 | 详情 | 详情 |