Preparation Of Biomass-Based Copper Catalytic Materials And Application In The Preparation Of Organoboron Compounds

Organic boron compounds have great application value in synthetic chemistry,and they are also an important building block in pharmaceutical preparation and synthetic chemistry.Many key drugs contain functional boron groups,and the C-B bonds in their structures can be converted into C-O,C-N,and C-C bonds by various paths.There are usually two difficulties in the preparation of organic boron compounds.One is the preparation process of borides,which typically uses simple alkenes or alkynes to undergo a boron addition reaction with diboron reagents to construct C-B bonds.However,the preparation process usually involves the use of transition metals and harsh conditions such as anhydrous and oxygen-free operations and expensive ligands and catalysts.Therefore,it is hoped to develop an environmentally friendly and green catalytic system to construct C-B bonds;The second is that many complex drug molecules have boron groups,but it is not common to construct C-B bonds from olefin molecules with complex functional groups.Currently,the existing methods for constructing CB bonds are not suitable for each type of olefin.Therefore,the purpose of this thesis is to solve the two major difficulties mentioned above,and to study the use of cellulose as a green substrate,supported by copper salts,to prepare heterogeneous catalytic materials,which can be used in the construction of C-B bonds,to achieve green synthesis of organic borides.Later,the transition metal nickel catalyzed three component boration of vinyl amides to synthesize organic borides was studied.The main work of this paper is:The first part of the work is to prepare cellulose supported cuprous oxide nanoparticles as catalytic materials(Cell@Cu Ti)And characterized the catalytic material using TG,XRD,XPS,SEM,TEM,etc Cell@Cu Ti apply to α,β-In the boron addition reaction of unsaturated olefins,using pure water as a solvent and under the action of(R)-(S)-josephos ligands,the target boron addition product was obtained in high yield and high enantioselectivity,with a yield of 80-97% and enantioselectivity of 85-98%.The reaction conditions were simple,without the need for anhydrous and oxygen-free operations and the addition of bases.A series of chalcone derivatives were synthesized using the "one pot method" strategy α,β-Unsaturatedβ-Hydroxyl compounds have achieved the conversion of C-B bonds to C-O bonds.The mechanism deuterization experiment was carried out to prove that the proton source required in the reaction was provided by pure water.The above research shows that the catalytic material has high reactivity,good substrate adaptation range,and excellent stability,and proposes a green and efficient catalytic material α,β-The strategy of unsaturated receptor boron addition reaction and the new method of copper catalyzed chiral boride synthesis have expanded the application range of cellulose and the types of biomass catalytic materials.In the second part,nickel catalyzed three component alkylboronation of vinyl amides was studied.Using vinyl amide as an olefin substrate,a series of alkyl bromines as electrophilic reagents,pinacol diborate as a boron source,cyclohexyl diamine ligands and nickel catalysts to catalyze the three-component boronation of olefins,electrophilic reagents,and boron sources,and simultaneously constructing C-C and C-B bonds on the olefin skeleton,the boronized product can be further converted into an antidepressant drug amphetamine,improving the application value of this method.The focus of this thesis is on the preparation and application of environmentally friendly cellulose supported metal copper catalytic materials α,β-In the boron addition reaction of unsaturated olefins,a variety of environmentally friendly organic borides have been successfully synthesized.As a heterogeneous catalyst,it has expanded the application range of cellulose,adding a green color to the industrial application of environmentally friendly materials,which has important theoretical and practical significance.A three-component boration reaction suitable for vinyl amide olefin compounds has also been developed,which can simultaneously construct C-C bonds and C-B bonds to efficiently synthesize organic boron compounds.