林文偉Lin, Wenwei柳彥成Liou, Yan-Cheng2023-12-089999-12-312023-12-082022https://etds.lib.ntnu.edu.tw/thesis/detail/a22e4da2a9b0e90657bd5ccbf9fb59b4/http://rportal.lib.ntnu.edu.tw/handle/20.500.12235/121030(一)穩定的鄰羥基對亞甲基苯醌化合物通過有機膦、醯氯和鹼處理，在無金屬且溫和條件下，有效合成官能化的苯并呋喃。同時，在催化條件下亦證明此一鍋化法之1,6-膦加成/氧-醯化/威悌反應，具有相似的合成官能化苯并呋喃的功效。(二)經由使用催化量的膦試劑進行分子內威悌反應，提供在無金屬條件下建構官能化 3-烯基苯并呋喃的有效方法。該一鍋化反應是通過將有機膦進行麥可加成到氧-醯化之硝基苯乙烯而引發，其中膦是通過用苯基矽烷對氧化膦進行化學選擇性還原而生成，從而產生膦葉立德，通過氧-醯化/亞硝酸消除/威悌反應製備多官能化的 3-烯基苯并呋喃衍生物。 (三)亞烷基米氏酸與亞胺葉立德經由硫脲片段衍生之金雞納鹼催化下，在短時間內進行 (3+2) 環加成/酯交換反應，在短時間內建構優異產率與鏡像選擇性之𠳭酮[4,3-b]吡咯啶衍生物。此外，我們根據實驗結果的發現，提出了催化劑與亞烷基米氏酸活化的反應模型。(一)An efficient synthesis of functionalized benzofurans is achieved under mild and metal free conditions from stable para-quinone methides by treatment with phosphine, acyl chloride, and a base. This one-pot phospha-1,6-addition/O-acylation/Wittig reaction is also demonstrated under catalytic conditions with similar efficacy.(二)A highly efficient protocol for the synthesis of functionalized 3-alkenyl benzofurans is demonstrated under metal-free conditions using catalytic amount of phosphine proceeding an intramolecular Wittig reaction. This one-pot reaction was initiated by the phospha-Michael addition of phosphine to O-acylated nitrostyrene, in which phosphine was in-situ generated from the chemoselective reduction of phosphine oxide with PhSiH3, would provide the phosphorus ylide to result in the aforementionedmultifunctionalized benzofuran via O-acylation/nitrous acid elimination/Wittig reaction.(三)A quinine-derived thiourea-catalyzed enantioselective (3+2) cycloaddition/desymmetrization transesterification reaction of Meldrum’s acid alkylidenes with azomethine ylides is realized in minute-scale. The desired chromeno[4,3-b]pyrrolidines were obtained in moderate to excellent yields with excellent stereoselectivities. Moreover, a plausible dual activation catalytic model via the hydrogen bonding interaction of the moiety of catalyst towards Meldrum’s acid alkylidene was proposed according to the findings in this study.苯并呋喃膦試劑分子內威悌反應對亞甲基苯醌3-烯基苯并呋喃催化膦威悌反應亞硝酸脫除亞胺葉立德米氏酸不對稱催化𠳭酮[43-b]吡咯啶para-Quinone methide16-Addition23-DiarylbenzofuranWittig reactionCatalytic Wittig reactionNitrous acid elimination3-AlkenylbezofuranChromeno[43-b]pyrrolidineAsymmetric catalystAzomethide ylideMeldrum’s acidetd