臺灣博碩士論文加值系統

本論文分為三部分：第一部分以苯硫基取代之1,3-丁二烯衍生物與多種亞胺鹽進行環化加成反應，生成含氮六員雜環化合物。硫取代基不僅增加雙烯的反應活性，並可完全控制反應的位置選擇性，僅得到氮環上硫取代基於對位的環化產物。第二部分則首創以苯硫基取代之1,3-丁二烯衍生物與苯?A基異氰酸酯進行碳氮雙鍵之環化加成反應的先例，生成pyridinone的環化產物。硫取代基不但增加雙烯活性，並可控制反應之化學與位置選擇性。環化產物且能進行加成、取代、脫除、烷化、溴化、去氮-苯?A基，以及去氮-苯?A基並烷化等反應，可得到許多不同結構的產物。第三部分則以苯硫基取代之1,3-丁二烯衍生物與缺電子羰基化合物進行環化加成反應，生成硫取代之含氧六員雜環化合物，其位置選擇性符合前沿分子軌域理論的預測。

This thesis contains three parts. The first part of the thesis studies the aza-Diels-Alder reactions of 2-(phenylthio)-1,3-butadienes with some simple iminium salts to give the piperidine or pipecolic acid derivatives. The thio-substituent not only enhances the reactivity of the diene, but also controls the regioselectivity of this reaction, giving only “para”-substituted cyclized products (with respect to the nitrogen).
The second part of the thesis reports the first aza-Diels-Alder reactions of arylsulfonyl isocyanates with thio-substituted 1,3-butadienes to give the pyridinone products. The thio-substituent on the diene increases the reactivity of the aza-Diels-Alder reaction together and controls the regio- and chemoselectivity. The cyclized products also undergo interesting reactions such as addition, substitution, elimination, alkylation, bromination, N-desulfonylation, N-desulfonylation-alkylation, etc.
The third part of the thesis studies the cycloaddition reactions of 2-(phenylthio)-1,3-butadienes with electron-deficient carbonyl dienophiles to give the 5,6-dihydro-2H-pyran derivatives. The regiochemistry is consistent with that predicted by the FMO theory.

封面
中文摘要
英文摘要
第一部分:硫取代之1,3-丁二烯衍生物與亞胺鹽的環化加成反應
緒論
結論
第二部分:硫取代?A環戊-3-烯與苯?A基異氰酸酯的環化加成反應及應用
緒論
結論
第三部分:苯硫基取代之1,3-丁二烯與缺電子羰基化合物的環化加成反應
緒論
結果與討論
實驗步驟與光譜數據
參考文獻

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