第一部份、合成香豆素為主體之雜雙環化合物及其潛在之應用
以香豆素為主體之系列雙環化合物衍生物主要是以對甲氧基苯胺和包含取代基之苯甲醛經由三到四個步驟合成。其中關鍵合成的步驟包含以酸催化氨醇11, 14, 16和4-羥基香豆素或4-胺基香豆素耦合作用反應得到閉環結構12, 17, 20和開環結構的15和21。當4-烷胺基香豆素作為耦合的主要試劑，主要的產物為進行環化作用的20。此外化合物17,20和21經由DDQ氧化可以形成quinone imine 18和22。此分子的結構經由X-ray 晶體繞射結構證實。
第二部份、經由多組成反應(MCR)合成氧氮雙環化合物及其應用於氧化還原開關
我們報導一個實用的方法在同一液相製備一系列的氧氮雙環化合物。目標產物以三氟甲磺酸鐿的催化會得到由中等到良好的產率範圍，藉由苯胺、酫、異丁酫和香豆素/奈醇/二甲基環己雙酮在一個反應槽進行連鎖反應。純化最終產物可以用乙酸乙酯與二氯甲烷結晶或管柱層析分離皆可輕易單離出大量的產物。以香豆素為主體的雙環化合物7h被有效的合成作為潛在螢光氧化還原開關。氧氮雙環化合物經由橋體連結放射螢光的香豆素與消光作用的苯胺將具有溶劑效應，雜雙環的一部份由氫硼化鈉造成開環結構使得螢光強度有明顯的減弱。開環結構8h可以經由雙氧水氧化回復為原始具有螢光的閉環結構7h。氧氮雙環化合物以螢光的作為化學開關的開與關經由雜雙環部份的開環結構與閉環結構。

Part I. Synthesis of coumarin-based heterobicycles and their potential applications
A series of bicyclic derivatives were prepared in three to four steps from p-anisidine and substituted benzaldehyde. The key step of the synthesis involved the acid-catalyzed coupling of 4-hydroxcoumarin or 4-aminocoumarin derivatives with amino alcohols 11, 14, 16 to give the ring-opened forms 12, 17, 20 and the ring-closed forms 15, 21. When 4-alkylaminocoumarins were used as the coupling reagents, the major cyclized product was 21, rather than the corresponding N-alkylated products. Alternatively, compounds 17, 20, 21 was cyclized by DDQ oxidation to produce the quinone imines 18, 22. The molecular structures of the synthesized compounds were characterized by X-ray crystallography.

Part II. Synthesis of the oxazabicyclic via MCRs and it’s application of fluorescence redox switches
A practical protocol for the preparation of a parallel solution-phase library of oxazabicycle is reported. Target compounds were obtained in moderate to good yields by a Yb(OTf)3-catalyzed, one-pot domino reaction from various anisidines, aryl aldehydes, isobutyraldehyde, and 4-hydroxycoumarins/dimedone. Purification of the final products by either recrystallization in ethyl acetate/methylene chloride or column chromatography allowed easy isolation of components of the array. a coumarin-based oxazobicyclic derivative 7h was efficiently synthesized as a novel fluorescence redox switch. The emission of the coumarin was found to be quenched by the aromatic amine, which had solvent effect when the fluorophore and the quencher were covalently connected via a rigid oxazobicyclic ring, the sodium borohydride-induced ring-opening of the heterobicyclic moiety results in a distinct decrease of the emission intensity. The resulting ring-opened form 8h can be reverted to the original fluorescence ring-closed form 7h via H2O2 oxidation. The fluorescence of the oxazobicycle can be chemically switched ON and OFF through the ring-closing and ring-opening of the heterobicyclic moiety.

目錄

誌謝………………………………………………………………………I
第一部份中文摘要………………………………………………………II
第二部份中文摘要………………………………………………………III
第一部分英文摘要………………………………………………………IV
第二部份英文摘要………………………………………………………V
目錄………………………………………………………………………VI
圖譜目錄………………………………………………………………VIII
圖表目錄…………………………………………………………………XII

第一部份、合成香豆素為主體之雜雙環化合物及其潛在之應用

壹、 緒論……………………………………………………………………2
貳、 結果與討論……………………………………………………………9
參、 結論……………………………………………………………………15
肆、 實驗部份
一、 儀器設備及試藥來源…………………………………………………16
二、 化合物的合成…………………………………………………………18
伍、 參考文獻………………………………………………………………27
陸、 光譜資料………………………………………………………………29

第二部份、經由多組成反應(MCR)合成氧氮雙環化合物及其應用於氧化還原開關

壹、 緒論……………………………………………………………………71
貳、 結果與討論……………………………………………………………76
參、 結論……………………………………………………………………82
肆、 實驗部份
一、 儀器設備及試藥來源…………………………………………………83
二、 化合物的合成…………………………………………………………85
伍、 參考文獻………………………………………………………………96
陸、 光譜資料………………………………………………………………98

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