Uç alkinler ile tiyollerin Cu(I) bağlanmış Schiff baz ağ polimeri katalizörü eşliğinde oksidatif çapraz dehidrojenatif birleştirme reaksiyonları

Alkynes are an important class of organic molecules because of their versatile applications in materials science and organic synthesis as building blocks. Sulfur-containing compounds have also a crucial role in synthetic organic chemistry since sulfur moiety acts as an important auxilary functional group. There has been an effort to combine these alkynes with sulfur-containing compounds by using metal-acetylides and sulfuryl halides or disulfides. However, these methods require a prefunctionalization progress of terminal alkyne or sulfur-containing coupling partners. This situation causes large number of side product formations which results in a dramatic decrease in the yields of reactions. Hence, the discovery of a new method to perform these reactions in high yields and better conditions gains a considerable attention. There are lots of studies on designing an useful catalyst to remove prefunctionalization processes and provide high yields and resusability. The term "catalysis" was first employed by Bezelius in 1836 tı ¸sdentify a new entity capable of promoting the occurrence of a chemical reaction by a "catalytic contact". In his view, the catalyst was seen as something that is added to the reaction to speed up the rate of the reactin (catalytic force) without being consumed or produced in the process. It is important to recognize that the catalysis can be traced back to the ancient terms. However, catalysis started to play a major impact on the chemical industry starting from the begining of twentieth century, nowadays more than 95 percent of chemicals being produced via a process that is at least includes at least one catalytic step. Traditionally, catalysts were distinguished into homogeneous and heterogeneous; subsequently, heterogenized catalysts were also introduced. This distinction is linked to the fact that the catalyst operates respectively in the same phase where the reaction occurs (homogenous catalysts) or in a different phase (heterogeneous or heterogenized catalysts). The main difference between a homogenous and heterogeneous catalyst is the fact that in case of homogeneous catalysts, every single catalytic entity can act as a single active site. This makes homogeneous catalysts more active and selective compared to traditional heterogeneous catalysts such as oxides or supported metal particles. A major drawback of the homogeneous catalysts is the difficulty of their recovery from the reaction medium. Precipitation with subsequent recovery or distillation of the reaction products, which is an energy intensie process, are typically needed in order to re-utilize homogeneous catalysts. Such operations may often deactivate the catalyst. Despite of these considerable advances, the problem with the homogeneous catalysis still remains to be unsolved. It is difficult to seperate catalyst from reaction mixture and reuse it. In contrast, design of an heteregenous catalysis should take increasingly more attention due to its possible advantages such as reusability, waste minimization derived from reaction workup and help to the development of green chemistry concept. xix Zhao et al. reported application of a hexagonally-ordered mesoporous material (MCM-41) supported bidentate nitrogen copper(I) complex [MCM-41-2N-CuCl] as a highly efficient and recyclable copper catalyst for the direct oxidative cross-dehydrogenative coupling of terminal alkynes with thiols using O2 as the sole oxidant under mild conditions to selectively afford a variety of alkynyl sulfides in good to excellent yields. According to their results, mesoporous material (MCM-41) has a extremely high surface area, large and uniform pore size, bidentate nitrogen copper complex can be easily formed and this complex can catalyze the coupling reaction between an alkyne and a thiol. In this thesis, the copper(I) incorporated microporous polymers' catalytic activity towards thiol-alkyne oxidative cross-dehydrogentavie coupling reactions without any prefunctionalization process was studied. In the first part of the thesis, the microporous network polymer was synthesized by melamine and terephtalaldehyde monomers through Schiff base chemistry. As known, the porous nature comes from the unique properities of monomers and frame of the polymer. In general, microporous organic polymers includes functional polar pendant groups such as amines, phenols or carboxylic acids since these groups can coordinate with metals. The rigid frame is also important for a ordered microporous structure. For that reason, aromatic conjugated structures or kinked aromatic high-performance polymers are used to have a rigid frame. Our choice of melamine and terephtalaldehyde as monomers is compatible with these criteria. Afterwards, the copper ions were incorporated into this microporous polymers and these materials were characterized. In the second part of the thesis, copper incorporated microporous Schiff base network polymer was used as a catalyst in the alkyne-thiol oxidative cross-dehydrogenative coupling reactions. The spectral and molecular weight analyses were applied to characterize the products.