金屬催化合成以及合成硫、硒異種原子之雜環分子庫

Abstract

本論文係藉由微波輔助及利用金屬活化碳氫鍵之兩種方式合成出不同架構的有機物小分子，並以此製備硫、硒類化合物。 實驗主要分為三個部分：第一部分係將本實驗室所合成的異香豆素 (isocoumarin)衍生物加入碘苯類化合物，在鈀金屬催化碳氫鍵的條件下形成異香豆素之衍生分子庫。 第二部分乃利用實驗室自行製備的異硒氰酸酯(isoselenocyanate)和3-氨基-4-氟苯甲酸甲酯在無金屬 (metal free)的條件下進行一步環化，最後再加入鹵烷進行烷化反應，此具有位向選擇性的反應可成功的在欲烷化的氮端上得到理想的異原子雜環苯並噁唑 (benzoxazle)之衍生物分子庫。接著根據第一部分的經驗，我們將酯基的部分利用金屬催化進行耦合反應，使得該分子成為同時具有異香豆素和苯並噁唑結構的衍生物。 第三部分則是利用微波輔助將異硫氰酸酯 (isothiocyanate)和5-苯甲基-1,3,6-三甲基嘧啶-2,4-(1H,3H)-二酮在鹼性的條件下一步環化生成嘧啶並吡咯奎若林二酮 (pyrimidopyrroloquinoxalinedione) 之衍生物。由於微波輔助的特性是以分子轉動生熱，使得我們可以快速的建立起分子庫。

Microwave assisted, metal catalysed carbon-hydrogen bond activation for the synthesize of various small molecules and attempts to prepare novel sulfur or selenium compounds. The thesis consists of three parts: First part consists of the C7-arylation of isocoumarins using arylhalide and palladium catalyst. Second part involves the synthesis of benzimidazole derivatives by performing the reaction of isoselenocyanate and Methyl 3-amino-4-fluorobenzoate under one-pot, metal-free condition. Further functionalization of N-alkylation has been carried out using various aliphatic and aromatic halides. After this reaction, isocoumarin derivatives also can be obtained by reacting with various alkynes under ruthenium catalyst. The third part explains the synthetic strategy involves the one pot cyclization of 5-benzoyl-1,3,6trimethylpyrimidine-2,4(1H,3H)-dione with isothiocyanate under microwave irradiation to obtain pyrimidopyrroloquinoxalinedione derivatives.