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【结 构 式】

【分子编号】24918

【品名】(5R)-1-(tert-butoxycarbonyl)-5-([[tert-butyl(diphenyl)silyl]oxy]methyl)-2-hydroxy-3-pyrrolidinecarboxylate

【CA登记号】

【 分 子 式 】C27H36NO6Si

【 分 子 量 】498.67148

【元素组成】C 65.03% H 7.28% N 2.81% O 19.25% Si 5.63%

与该中间体有关的原料药合成路线共 1 条

合成路线1

该中间体在本合成路线中的序号:(X)

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
Extended Information