由2-硫代甲醚□喃合成r-內酯衍生物之研究

Abstract

由2-硫代甲醚□喃合成 g-內酯衍生物之研究 Synthesis of g-butyrolactone derivatives from 2-methylthiofuran 研究生：謝閔凔 指導教授：吳獻仁博士 國立交通大學應用化學研究所 中文摘要 具有2-乙醯氧基-g-丁內酯 (2-acetoxy-g-butenolide) 及2-羧基-g-丁內酯 (2-Carboxy-g-butyrolactone) 這兩種g-內酯骨架的化合物在很多天然物常見到，相關的文獻更是多不勝數。近來本實驗室發展了一個合成方法，利用本實驗室之前的研究，以g-羰基-a,b-不飽和硫代酯2為Michael accepter可與不同Michael donor進行的Michael加成反應，接著再利用硼氫化鈉還原可形成g-內酯衍生物，我們發現若Michael donor為□喃時，形成加成產物後，可利用臭氧裂解反應破壞加成產物上的□喃環，進而形成2-羧基-g-丁內酯化合物，若Michael donor為硫代酚時，合成g-內酯衍生物後，我們可進行氧化反應及Pummerer反應引進乙醯氧基進而形成2-乙醯氧基-g-丁內酯，若Michael donor為2-硫代甲醚□喃時，合成g-內酯衍生物後，經過PCC氧化反應氧化2-硫代甲醚□喃環，我們可以合成一個特異的g-丁內酯化合物17及18。

Synthesis of g-butyrolactone derivatives from 2-methylthiofuran Student : Hsieh, Min-chang Advisor : Dr. Wu, Hsien-Jen Institute of Applied Chemistry National Chiao Tung University Abstract Synthesis of 2-acetoxy-g-butenolide and 2-carboxy-g-butyrolactone derivatives is very important in total synthesis of natural products. Many organic chemists have done much work about this. Recently, we discovered a new methodology for synthesis the skeleton of 2-acetoxy-g-butenolide and 2-carboxybutyrolactone. According to our research, we could use compound 2 as a Michael acceptor to react with different Michael donor to get the Michael addition products. Taking the addition products react with sodium borohydride, we could get g-lactone derivatives. We used furan as a Michael donor to get the addition products, then used ozone as an oxidative reagent to fragmente the furan ring. After some steps, we could synthesis the 2-carboxybutyrolactone derivatives. We also used thiophenol as a Michael donor to synthesis the g-lactone derivatives. After the m-CPBA oxidative reaction and Pummerer reaction, we could synthesize the 2-acetoxy-g-butenolide derivatives. When we used 2-methylthiofuran as a Michael donor to synthesize the g-lactone derivatives, after the PCC oxidation, we could synthesize the novel g-lactone derivatives 17 and 18.