一、透過有機鏻鹽經由分子內Wittig反應合成雙取代異噁唑 二、透過亞胺葉立德及1,3-茚滿二酮亞芐基進行位向選擇性之 (3+2) 環加成反應合成具有高鏡像選擇性的chromeno[3,4-b]pyrrolidines

I. Phosphine-Mediated Synthesis of Di-substituted Isoxazoles via Intramolecular Wittig Reaction II. A highly enantioselective synthesis of chromeno[3,4-b]pyrrolidines via regioselective (3+2) cycloaddition of azomethine ylides and indandionebenzylidines

林意蓉(Lin Yi-Jung)

指導教授 ： 林文偉

國立臺灣師範大學/理學院/化學系/碩士(2018年)

https://doi.org/10.6345/THE.NTNU.DC.012.2018.B05

摘要

第一章、透過有機鏻鹽經由分子內 Wittig 反應合成雙取代異噁唑
　　經由一連串反應條件優化，成功地透過本實驗室先前開發出製備呋喃、噁唑化合物之合成策略應用於合成具有生物活性之異噁唑衍生物，我們利用穩定、製備方法簡單的有機鏻鹽作為起始物，在溫和的反應條件下建立出一個高效率的氧醯化反應、分子內Wittig反應合成雙取代異噁唑，甚至透過一鍋化反應表現仍不遜色。

第二章、透過亞胺葉立德及1,3-茚滿二酮亞芐基進行位向選擇性之 (3+2) 環加成反應合成具有高鏡像選擇性的chromeno[3,4-b]pyrrolidines
藉由亞胺葉立德及1,3-茚滿二酮亞芐基合成出連續四個立體中心之chromeno[3,4-b]pyrrolidines，並透過金雞納鹼雙官能催化劑之氫鍵催化模式下進行 (3+2)環加成反應達到位向選擇性之目的以及合成出具有高立體選擇性之產物chromeno[3,4-b]pyrrolidines。並透過將產物進行衍生化解決了產物光譜判定之困難以及非鏡像異構物之判別不易的問題並建構出具有藥用的化合物。

關鍵字

有機鏻鹽 ； 異噁唑 ； 亞胺葉立德 ； 位向選擇性 ； 高鏡像選擇性

並列摘要

I. Phosphine-Mediated Synthesis of Di-substituted Isoxazoles via Intramolecular Wittig Reaction
Motivated by the successful synthesis of the furans and oxazoles, we herein extend our intramolecular Wittig reaction strategy to construct potentially bio-active isoxazoles. To begin with, a series of stable isolable phosphonium salts were generated from α-halo ketoximes and the thus obtained phosphonium salts were subjected to a tandem O-acylation and intramolecular Wittig reaction to afford isoxazoles under mild conditions. Further, a one-pot protocol was also realized wherein the α-halo ketoximes were directly transformed into isoxazoles in moderate to good yields.

II. A highly enantioselective synthesis of chromeno[3,4-b]pyrrolidines via regioselective (3+2) cycloaddition of azomethine ylides and indandionebenzylidines
Scarcely reported chromeno[3,4-b]pyrrolidines bearing four contiguous stereocenters were synthesized starting from azomethine ylides and indandionebenzylidines. Cinchona alkaloid derived bifunctional hydrogen bonding catalyst was found to promote this regioselective (3+2) cycloaddition to generate the above products in good yields with high enantio and diastereoselectivities. Further derivatization of the adducts was not only helpful in determining the diasteromeric ratio of the adducts but also in demonstrating the synthetic utility of the protocol.

並列關鍵字

phosphonium salt ； isoxazole ； azomethine ylide ； regioselective ； enantioselective ； chromeno[3,4-b]pyrrolidines

參考文獻

第一章

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