(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

I. Synthesis of Functionalized Benzofurans from para-Quinone Methides via Phospha-1,6-Addition/O-Acylation/Wittig Pathway II. Phosphine-catalyzed Chemoselective Reduction/Elimination/Wittig Reaction Sequence for Synthesis of Functionalized 3-Alkenyl Benzofurans III. Enantioselective Construction of Chromeno[4,3-b]pyrrolidines from Meldrum’s Acid Alkylidenes and Azomethide Ylides via the (3+2) Cycloaddition/Lactonization Pathway

柳彥成(Liou Yan-Cheng)

指導教授 ： 林文偉

國立臺灣師範大學/理學院/化學系/博士(2022年)

https://doi.org/10.6345/NTNU202201092

摘要

(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

關鍵字

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

並列摘要

(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 aforementioned multifunctionalized 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.

並列關鍵字

para-Quinone methide ； 1,6-Addition ； 2,3-Diarylbenzofuran ； Wittig reaction ； Catalytic Wittig reaction ； Nitrous acid elimination ； 3-Alkenylbezofuran ； Chromeno[4,3-b]pyrrolidine ； Asymmetric catalyst ； Azomethide ylide ； Meldrum’s acid

參考文獻

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