https://scholars.lib.ntu.edu.tw/handle/123456789/178503
標題: | 單體非重複之寡聯芳香環與四取代呋喃化合物 Furan-Containing Oligoaryls without Repetitive Units and Tetrasubstituted Furans |
作者: | 陳嘉弘 Chen, Jia-Hong |
關鍵字: | 呋;喃;三氟醋酸;炔丙基硫縮酮;Furan;TFA;Propargylic dithioacetal | 公開日期: | 2006 | 摘要: | 炔丙基硫縮酮經有機金屬試劑進行親硫性開環,與醛類化合物反應產生丙二烯醇中間體,於酸性條件下進行分子內環化反應,可生成呋喃與苯環交錯之寡聯芳香環化合物。利用一系列官能基化的炔丙基硫縮酮進行此一鍋式呋喃稠合反應,產生相對應之寡聯芳香環化合物,可進一步利用官能基轉換,應用於苯環兩端向外延伸的分子線之合成。值得注意的是當有酯基存在時,炔丙基硫縮酮仍可作為碳硫鍵之極性逆轉體。應用會集式合成策略,改變苯環兩端向外延伸的方法,可使分子線長度的延伸得以倍數增長。藉由此合成手法,改變單體炔丙基上的取代基,可合成出單體非重複之共軛奈米分子線。 除了藉由三氟醋酸來推動丙二烯醇中間體的合環反應外,醋酸汞亦能夠提供新的反應途徑合成呋喃化合物。其呋喃環上的汞則能夠以一鍋化的方式置換成碘,藉此製備出一系列含碘之呋喃化合物。酯基、烷基、芳香基……等官能基皆能在這樣的反應條件下存在而不分解。結合不同類型的耦合反應,可藉此合成出具位向選擇性的四取代呋喃化合物。 A new one-pot furan annulation from corresponding propargylic dithioacetals and aldehydes has been reported recently. The bidirectional growth approach was also employed to the one-pot furan annulation for the synthesis of higher homologues towards molecular wires. It is noticeable that propargylic dithioacetal moiety could still serve as carbon-sulfur bond umpolung even in the presence of an ester group. The iterative divergent/convergent doubling approach provide an efficient strategy for the synthesis of benzene/furan alternating oligoaryls by utilizing our one-pot furan annulation reaction. The substituents on the furan rings can be easily varied by changing the substituents in the starting propargylic dithioacetals. This route provides a useful procedure for the synthesis of alternating benzene/furan oligomers without repetitive units. A convenient procedure for highly regioselective synthesis of tetrasubstituted furans from the corresponding propargylic dithioacetals is described. Treatment of propargylic dithioacetals with n-BuLi and an aldehyde followed by mercuric acetate-promoted annulation and desulfurization affords the corresponding mercurio-substituted furans. Subsequent replacement of the mercuric moiety with iodine and potassium iodide yield the corresponding 2,4,5-trisubstituted-3-iodofurans. It is noteworthy that although these reactions are multistage, it can be accomplished in one pot. Transition-metal catalyzed cross-coupling reactions of the iodofurans furnish a variety of fully substituted furans. |
URI: | http://ntur.lib.ntu.edu.tw//handle/246246/52008 | 其他識別: | zh-TW |
顯示於: | 化學系 |
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ntu-95-R93223068-1.pdf | 23.31 kB | Adobe PDF | 檢視/開啟 |
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