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【结 构 式】 
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【分子编号】54892 【品名】3-{[(E)-2-butenyloxy]methyl}-4-iodo-2-methoxy-6-(trimethylsilyl)pyridine; (E)-2-butenyl [4-iodo-2-methoxy-6-(trimethylsilyl)-3-pyridinyl]methyl ether 【CA登记号】 |
【 分 子 式 】C14H22INO2Si 【 分 子 量 】391.32419 【元素组成】C 42.97% H 5.67% I 32.43% N 3.58% O 8.18% Si 7.18% |
合成路线1
该中间体在本合成路线中的序号：(XXXII)The silylated pyranopyridine (XXXIV) was prepared by an analoguos route to that of Scheme 3 starting from 2-methoxy-6-(trimethylsilyl)pyridine (XXX). Halogenation-desilylation of (XXXIV) by means of ICl-furnished iodide (XXXV). Subsequent demethylation of (XXXV) to give lactam (XXXVI) was performed employing either aqueous HI or iodotrimethylsane. Alkylation of lactam (XXXVI) with 1,4-dichloro-2-butyne (XXXVII) to (XXXVIII), followed by reaction with piperazine (IX), yielded (XXXIX). The cascade radical cyclization of (XXXIX) with isonitrile (XL) under sunlamp irradiation in the presence of hexamethyldistannane led to an inseparable mixture of the title compound and its regioisomer (XLI).
| 【1】 Josien, H.; et al.; A general synthetic approach to the (20S)-camptothecin family of antitumor agents by a regiocontrolled cascade radical cyclization of aryl isonitriles. Chemistry (Weinheim) 1998, 4, 1, 67. |
| 【2】 Curran, D.P.; et al.; Cascade radical reactions of isonitriles: A second-generation synthesis of (20S)-camptothecin, topotecan, irinotecan, and GI-147211C. Angew Chem. Int Ed 1995, 34, 23-24, 2683. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IX) | 10061 | 1-Methylpiperazine; 1-Methyl piperazine; N-Methylpiperazine | 109-01-3 | C5H12N2 | 详情 | 详情 |
| (XIX) | 54879 | 2-(dimethylamino)ethyl(methyl)formamide | C6H14N2O | 详情 | 详情 | |
| (XXII) | 54882 | 2-Butene-1-ol; Crotyl Alcohol; trans-Propenylcarbinol | 504-61-0 | C4H8O | 详情 | 详情 |
| (XXX) | 54890 | methyl 6-(trimethylsilyl)-2-pyridinyl ether; 2-methoxy-6-(trimethylsilyl)pyridine | C9H15NOSi | 详情 | 详情 | |
| (XXXI) | 54891 | 4-iodo-2-methoxy-6-(trimethylsilyl)nicotinaldehyde | C10H14INO2Si | 详情 | 详情 | |
| (XXXII) | 54892 | 3-{[(E)-2-butenyloxy]methyl}-4-iodo-2-methoxy-6-(trimethylsilyl)pyridine; (E)-2-butenyl [4-iodo-2-methoxy-6-(trimethylsilyl)-3-pyridinyl]methyl ether | C14H22INO2Si | 详情 | 详情 | |
| (XXXIII) | 35096 | 4-ethyl-6-(trimethylsilyl)-1H-pyrano[3,4-c]pyridin-8-yl methyl ether; 4-ethyl-8-methoxy-6-(trimethylsilyl)-1H-pyrano[3,4-c]pyridine | C14H21NO2Si | 详情 | 详情 | |
| (XXXIV) | 54893 | (4S)-4-ethyl-4-hydroxy-8-methoxy-6-(trimethylsilyl)-1,4-dihydro-3H-pyrano[3,4-c]pyridin-3-one | C14H21NO4Si | 详情 | 详情 | |
| (XXXV) | 54894 | (4S)-4-ethyl-4-hydroxy-6-iodo-8-methoxy-1,4-dihydro-3H-pyrano[3,4-c]pyridin-3-one | C11H12INO4 | 详情 | 详情 | |
| (XXXVI) | 49255 | (4S)-4-ethyl-4-hydroxy-6-iodo-1H-pyrano[3,4-c]pyridine-3,8(4H,7H)-dione | C10H10INO4 | 详情 | 详情 | |
| (XXXVII) | 50923 | 1,4-Dichloro-2-butyne | 821-10-3 | C4H4Cl2 | 详情 | 详情 |
| (XXXVIII) | 54895 | (4S)-7-(4-chloro-2-butynyl)-4-ethyl-4-hydroxy-6-iodo-1H-pyrano[3,4-c]pyridine-3,8(4H,7H)-dione | C14H13ClINO4 | 详情 | 详情 | |
| (XXXIX) | 54886 | (4S)-4-ethyl-8-methoxy-3,4-dihydro-1H-pyrano[3,4-c]pyridine-3,4-diol | C11H15NO4 | 详情 | 详情 | |
| (XL) | 54898 | C9H7NO2 | 详情 | 详情 | ||
| (XLI) | 54897 | (9S)-9-ethyl-9-hydroxy-16-[(4-methyl-1-piperazinyl)methyl]-2,3-dihydro-12H-[1,4]dioxino[2,3-f]pyrano[3',4':6,7]indolizino[1,2-b]quinoline-10,13(9H,15H)-dione | C28H30N4O6 | 详情 | 详情 |