Research On The Construction Of Substituted Oxazole/Triazole Catalyzed By Copper

Heterocyclics are very important structure units in many natural product molecules,which are currently the largest number of organic compounds.Compounds,with its specific chemical structure and biological activity,which contain oxazole ring and triazole ring,are widely used in the biomedical,organic chemistry fields.Hence,the study on the synthesis strategies of these compounds has been attracted much more attentions.Besides,synthesis of organic heterocycles catalyzed by transition metal is highly efficient and convenien,and has become much more useful tactics for the constructions of heterocyclic compounds.However,precious metal catalysts are usually more expensive and more toxic.In contrast,metal copper reagents are efficient and low toxic,and play an increasingly important role in the field on construction of heterocyclics.In addition,taking into account of the catalysts whitch are recycled and reusable,heterogeneous catalysis has become another research boom.Therefore,from the environmentally friendly and green chemistry point of view,in this paper,a method on the synthesis of oxazole ring catalyzed by copper salt will be explored,and the synthesis of trizine ring catalyzed by heterogeneous catalyst will be discussed.Chapter One The brief description of heterocyclic compounds and copper-catalyzed the synthesis of heterocyclic compounds are summarized.Chapter Two The progress of the synthesis of oxazole ring and the decarboxylation/cross-coupling reaction of ?-keto acid in recent years and the cyclic addition/decarboxylation experiments between ?-keto acid and methyl isocyanine were introduced.The 5-aryl oxazole was synthesized efficiently by CuCl/1,10-phenanthrolinecatalyzed by tandem [3+2] cycloaddition/decarboxylation between ?-keto acid and methyl isocyanine.A series of C5-substituted oxazole derivatives were obtained under the optimal conditions.The mechanism of the reaction was deduced by free radical control experiment.It was found that ?-keto acid was self-decarboxylated during the reaction process,and thus the use ofa large number of oxidants was avoided,to develop a new way of ?-keto acid to provide acyl reagents when participated in the reaction.Chapter Three The progress of CuAAC reaction and the progress of catalysts for supported Zr-MOF were introduced and the experiment of CuBr₂@Zr-MOF heterogeneous catalytic three-component "Click" reaction was introduced.The CuBr₂@Zr-MOF with heterogeneous catalytic potential was prepared by loading CuBr₂ with high catalytic activity in the high stability MOFs skeleton.The loading of the central metal copper was determined by PXRD and ICP test.The catalytic performance of the three-component "click" reaction between benzene boric acid,sodium azide and phenylacetylene was studied,and the aryl boronic acid and alkyne containing various substituents were investigated for its universality.After the catalyst was used four times,the copper loading was not lost,and the catalytic activity was not significantly reduced,and thus a new use of CuBr₂@Zr-MOF was developed.Chapter Four Summarizes the main work of this paper and prospects the research prospects of this subject.