四丁基氟化銨及無機鹼催化硫醇與α‚β-不飽和酸化合物進行加成反應之研究探討

Abstract

本論文主要分為兩個章節，第一章節為探討以α‚β-不飽和酸化合物為受質進行1,4-共軛加成反應的研究。而根據以往文獻所報導的研究結果中發現，當以α‚β-不飽和酸化合物為受質進行加成反應時，往往所獲得的產物產率皆為偏低，或同時會有其它副產物的生成。在此，本研究發展出以四丁基氟化銨為催化劑，催化硫醇與α‚β-不飽和酸化合物進行1,4-共軛加成反應，可獲得高產率的單一加成產物。 第二章節則為探討利用無機鹼催化硫醇對具有吲哚結構的α‚β-不飽和酸化合物進行加成反應，可得到高產率之去羧基化的3-(1-(thiol)ethyl)-1H-indoles產物。

The present work has been divided into two chapters, the first chapter deals with the 1,4-conjugate addition of thiols to α,β-unsaturated carboxylic acids catalyzed by a mild base tetrabutylammonium fluoride(TBAF). Herein, we have described a novel procedure for the synthesis of 3-sulfanylpropionic acid, which is often encountered in molecules of biologically active compounds. The reaction conditions described here are simple, mild, and efficient. The use of TBAF as a base has the advantages of being economically viable and more efficient for the conjugative addition. The reaction system can be successfully applied to a variety of α,β-unsaturated acids as well as thiols to synthesize a wide variety of sulfur containing carboxylic acids in excellent yields. The second chapter illustrates the potassium hydroxide or potassium carbonate catalyzed conjugative addition of thiols to (3-(1H-indol-3-yl)acrylic acids leading to the formation of 3-(1-(aryl/alkylthio)ethyl)-1H-indoles via decarboxylation of the adduct. A wide range of thiols and (3-(1H-indol-3-yl)acrylic acids reacted under the present reaction conditions to produce 3-(1-(aryl/alkylthio)ethyl)- 1H-indoles in excellent yields.