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【结 构 式】 
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【分子编号】24931 【品名】5-hexenoyl chloride 【CA登记号】 |
【 分 子 式 】C6H9ClO 【 分 子 量 】132.58956 【元素组成】C 54.35% H 6.84% Cl 26.74% O 12.07% |
合成路线1
该中间体在本合成路线中的序号：(XXII)The ketalization of (XVII) with methyl orthoformate in methanol gives the dinethylketal (XVIII), which is condensed with 3-butenyllithium (XIX) to afford the tetracyclic compound (XX). A new cyclization of (XX) by means of a ruthenium catalyst closes the macrocycle of (XXI), which is condensed with 5-hexenoyl chloride (XXII) and triethylamine affording the precursor (XXIII) of the cyclooctane ring found in the target compound. The cyclization of (XXIII) with the same ruthenium catalyst gives the intermediate (XXIV) with the ring system of the target compound, which is finally reduced with DIBAL in order to eliminate the extra oxygen of (XXIV), and oxidized again with Dess Martin periodinane (DMP) to regenerate the formyl group reduced by the DIBAL to yield the target ircinal A.
| 【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 |
|---|---|---|---|---|---|---|
| (XVII) | 24926 | 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 | |
| (XVIII) | 24927 | tert-butyl (2R,3aR,7aR,10aR)-8-(dimethoxymethyl)-5-(5-hexenyl)-10-oxo-2-vinyl-2,3,5,6,7,7a,10,10a-octahydropyrrolo[2,3-i]isoquinoline-1(4H)-carboxylate | C27H42N2O5 | 详情 | 详情 | |
| (XIX) | 24928 | 4-pentenyllithium | C5H9Li | 详情 | 详情 | |
| (XX) | 24929 | (4aR,6aS,10R,11aR,11bR)-6a-(3-butenyl)-5-(dimethoxymethyl)-2-(5-hexenyl)-10-vinyl-2,3,4,4a,6a,10,11,11b-octahydro-1H-[1,3]oxazolo[5,4,3-hi]pyrido[3,4-d]indol-8-one | C27H40N2O4 | 详情 | 详情 | |
| (XXI) | 24930 | (1S,13R,14R,16R,23R)-21-(dimethoxymethyl)-16-vinyl-19-oxa-10,17-diazapentacyclo[11.6.2.1(1,14).1(10,14).0(17,23)]tricosa-4,20-dien-18-one | C25H36N2O4 | 详情 | 详情 | |
| (XXII) | 24931 | 5-hexenoyl chloride | C6H9ClO | 详情 | 详情 | |
| (XXIII) | 24932 | 1-[(1R,13S,14R,16R,18R)-19-(dimethoxymethyl)-13-hydroxy-16-vinyl-4,15-diazatetracyclo[11.5.2.1(4,18).0(14,18)]henicosa-9,19-dien-15-yl]-5-hexen-1-one | C30H46N2O4 | 详情 | 详情 | |
| (XXIV) | 24933 | (1R,2R,4R,12R,13S)-13-hydroxy-10-oxo-11,22-diazapentacyclo[11.11.2.1(2,22).0(2,12).0(4,11)]heptacosa-5,16,25-triene-25-carbaldehyde | C26H36N2O3 | 详情 | 详情 | |
| (XXV) | 24934 | (1R,2R,4R,12R,13S)-25-(hydroxymethyl)-11,22-diazapentacyclo[11.11.2.1(2,22).0(2,12).0(4,11)]heptacosa-5,16,25-trien-13-ol | C26H40N2O2 | 详情 | 详情 |