利用有機膦試劑誘導肉桂酸極性反轉以合成呋喃酮衍生物

Abstract

本論文可以分為兩個主題，利用有機膦試劑誘導肉桂酸極性反轉以合成呋喃酮衍生物以及探討利用有機膦試劑誘導 β 位醯化反應以有效率合成己-4-烯-1,3,6-三酮衍生物。

第一部分： 在溫和條件下，藉由有機膦試劑促使肉桂酸衍生物形成具有烯酮部分的磷葉立德中間體，除此之外，反應都是以一鍋化的形式進行，省去繁瑣的起始物製備，反應過程中也意外地合成出呋喃酮衍生物。開發具有多功能性的中間體在有機合成上有著重要的價值，此部分嘗試開發新穎的合成方法及發展具有多功能性的烯酮部分的磷葉立德中間體。

第二部分： 透過有機膦試劑與一系列鏈狀的 α,β-不飽和雙酮衍生物反應，Michael 加成之後再經由氧-醯化反應以及鹼的作用下，能夠在親電性的 β 位建構一個醯基，成功的在兩個親電性碳之間形成鍵結，而且反應條件溫和，沒有金屬參與，產率最高可達 85%，並藉由控制實驗對此機制進行探討。This thesis is divided into two parts: synthesis of furanone derivatives via umpolung by organophosphanes (part I) and investigation of phosphine-mediated direct β-acylation reactions: An efficient method for the synthesis of hex-4-en-1,3,6-trione derivatives (part II).

Part I: We have developed an organophosphane-mediated cinnamic acid derivatives for synthesis of the ylide which contain ketene group in mild condition. In addition, the advantages of the reaction are one-pot, without reactants preparation. We accidentally obtain furanone derivatives.It is important for the development of versatile intermediates in organic synthesis. So we attempt to develop novel synthetic methods and valuable ketene intermediate in this part.

Part II: Construction an acyl group at the electrophilic β position of α,β-unsaturated diketone derivatives by organophosphane has been achieved. The reaction condition is mild, metal free and could afford good yields.