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【结 构 式】 
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【分子编号】24922 【品名】1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aS)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)-4-oxo-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate 【CA登记号】 |
【 分 子 式 】C56H74N2O7Si2 【 分 子 量 】943.38384 【元素组成】C 71.3% H 7.91% N 2.97% O 11.87% Si 5.95% |
合成路线1
该中间体在本合成路线中的序号：(XIV)The reaction of protected pyrrolidone (VIII) with LHMDS and CO2 affords the corresponding pyrrolidonecarboxylic acid (IX), which is reduced at the ketonic oxygen with NaBH4 providing the hydroxyacid (X). The condensation of the previously obtained amino acid (VII) with the acid (X) by means of oxalyl chloride and triethylamine affords amide (XI), which is condensed with vinyltributylstannane (XII) by means of Pd(PPh3)4 to give the butaiene derivative (XIII). The spontaneous Diels-Alder cyclization of (XIII) yields the tricyclic compound (XIV), which is oxidized with CrO3 to the dione (XV). The deprotection of the hydroxyl groups of (XV), their reaction with oxalyl chloride and with methylenetriphenylphosphorane provides compound (XVI) with two terminal reactive double bonds. The reduction of (XVI) with DIBAL, followed by oxidation with Dess Martin periodinane (DMP) affords the corresponding aldehyde (XVII).
| 【1】 Martin, S.F.; et al.; Enantioselective total synthesis of ircinal A and related manzamine alkaloids. J Am Chem Soc 1999, 121, 4, 866. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| 27301 | methylene(triphenyl)phosphorane | C19H17P | 详情 | 详情 | ||
| (VII) | 24915 | methyl (Z)-2-bromo-5-[(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)amino]-2-pentenoate | C27H38BrNO3Si | 详情 | 详情 | |
| (VIII) | 24916 | tert-butyl (2R)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-oxo-1-pyrrolidinecarboxylate | C26H35NO4Si | 详情 | 详情 | |
| (IX) | 24917 | (5R)-1-(tert-butoxycarbonyl)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2-oxo-3-pyrrolidinecarboxylate | C27H34NO6Si | 详情 | 详情 | |
| (X) | 24918 | (5R)-1-(tert-butoxycarbonyl)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2-hydroxy-3-pyrrolidinecarboxylate | C27H36NO6Si | 详情 | 详情 | |
| (XI) | 24919 | tert-butyl (2R)-4-[[[(E)-4-bromo-5-methoxy-5-oxo-3-pentenyl](5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)amino]carbonyl]-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2,3-dihydro-1H-pyrrole-1-carboxylate | C54H71BrN2O7Si2 | 详情 | 详情 | |
| (XII) | 24920 | tributyl(vinyl)stannane；Tributylvinylstannane;Vinyltributylstannane | 7486-35-3 | C14H30Sn | 详情 | 详情 |
| (XIII) | 24921 | tert-butyl (2R)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-4-([(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)[(3Z)-4-(methoxycarbonyl)-3,5-hexadienyl]amino]carbonyl)-2,3-dihydro-1H-pyrrole-1-carboxylate | C56H74N2O7Si2 | 详情 | 详情 | |
| (XIV) | 24922 | 1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aS)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)-4-oxo-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate | C56H74N2O7Si2 | 详情 | 详情 | |
| (XV) | 24923 | 1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aR)-2-([[tert-butyl(diphenyl)silyl]oxy]methyl)-5-(5-[[tert-butyl(diphenyl)silyl]oxy]pentyl)-4,10-dioxo-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate | C56H72N2O8Si2 | 详情 | 详情 | |
| (XVI) | 24924 | 1-(tert-butyl) 8-methyl (2R,3aS,7aR,10aR)-5-(5-hexenyl)-4,10-dioxo-2-vinyl-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1,8(4H)-dicarboxylate | C26H36N2O6 | 详情 | 详情 | |
| (XVII) | 24925 | tert-butyl (2R,3aR,7aR,10aR)-8-formyl-5-(5-hexenyl)-10-oxo-2-vinyl-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1(4H)-carboxylate | C25H36N2O4 | 详情 | 详情 |