(一) 使用鄰羥基對亞甲基苯醌經由 1,6-膦加成/氧-醯化/威悌反應建構官能化苯并呋喃衍生物(二) 膦催化之化學選擇性還原/亞硝酸離去/威悌反應建構 3-烯基苯并呋喃衍生物(三) 亞烷基米氏酸與亞胺葉立德經 (3+2) 環加成/內酯化反應合成高鏡像選擇性之𠳭酮[4,3-b]吡咯啶

Abstract

(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.