本論文第一部分將探討銠金屬搭配2,2''-雙二苯膦基-1,1''-聯萘(BINAP)在水為溶劑的條件下進行芳香基碘化物與硫醇之交互耦合反應。此催化系統也可以製備乙烯基硫醚化合物。 第二部分則是探討碳-硒鍵的生成反應。主要分成兩方向進行研究：(i) 以吲哚作為起始物與二硒化物，進行交互耦合反應，可以合成多種含有芳香基硒醚取代的吲哚衍生物，我們也初步研究這一類化合物的生物活性；(ii) 具有拉電子基的芳香基鹵化物或吡啶鹵化物都可以直接與二硒化物進行交互耦合反應而得到芳香基硒醚化合物，值得一提是，無論是2號或3號碳上有碘、溴、氯及氟取代基的吡啶都能與二硒化物進行碳-硒鍵的生成。 In the first part of this thesis, we report that a combination of rhodium salt with BINAP can be served as a powerful catalyst for coupling thiols with aryl iodides in water. Moreover, this catalytic system is allocable to couple vinyl halides with thiols. The second part of this thesis, we found that C-Se bond can be formed smoothly under transition-metal-free conditions. First, indoles are introduced as the coupling partners to couple with diselenides, giving the corresponding aryl selenides in good to excellent yields; we also studied the bioactivity of these compounds. Second, we discovered that the electron-withdrawing-containing aryl halides and nitrogen-containing heteroaryl halides can be smoothly coupled with aryl selenides to form diaryl selenides under metal-free conditions. Notably, either 2 or 3 halogenated pyridines can be conducted with diselenides to provide the coupling products in good yields.