The New Methodology Study On The Transition-Metal-Catalyzed Synthesis Of Carbonyl Compound Based On The C-H Bond Activation/C-C Bond Cleavage Under Oxygen

The carbonyl-containing compounds as one of widely existing compouds in nature,play an irreplaceable role in organic synthesis, medicinal chemistry, biological materials, catalytic industry and so on. Among them, α-ketoesters are the prevailing skeletons of many bioactive compounds and are important precursors as well in organic synthesis. More and more chemists have been attracted toward this novel field. However, there are some obvious drawbacks in the precedent reports, such as the lack of atom economy, expensive synthetic raw materials, and the harsh reaction conditions, which strongly restrict the rapid development. Aromatic esters and amides as the most common carbonyl compounds are also widely applied in industry.The traditional synthetic methods towards these two types of compounds include direct coupling between organic acids and alcohols or ammonia, substitution reaction between carboxylates and chlorinated hydrocarbons, the alcoholysis or ammonolysis of nitriles, and transesterification or transamidation. However, there are some inevitable defects among the above four most traditional methods. With the lack of human environmental resources, more and more attentions have been paid into the ecological environment protection issues, therefore it becomes highly desirable yet very challenging to find more efficient, cheaper, lower toxic, green and sustainable method. In this thesis, we will explore the novel synthetic methods on activation of C-H bond or the cleavage of C-C bond to construct the carbonyl-containing compounds via cheap transition metal-catalyzed reaction, with acetophenones and benzene acetonitriles as starting materials and environmental benign oxygen as the terminal oxidant.In recent times, it has become a hot topic on sustainable transformation with transition metal as catalyst in modern synthetic organic chemistry. In the past few decades, great progress has been made with palladium, rhodium and other expensive transition metal as a catalyst in organic transformations. However, cheap transition metal Cu or Fe catalyzed aerobic oxidative formation of carbonyl-containing compounds is still a great challenge These two types of transition metals have manyadvantages: low toxicity, inexpensiveness, easy preparation, good compatibility, mild reaction condition. However, how to improve the catalytic activity and realize the selectivity is still a big challenge.In this thesis, we developed some novel methods by using copper or iron salts as catalysts, acetophenones and benzene acetonitriles as starting materials, oxygen as the terminal oxidant, to construct a variety of carbonyl compounds. These strateges were featured with high efficiency, inexpensiveness, low toxicity, mildness and sustainability, and they could be scaled-up easily without loss the efficiency,therefore they might have potential application in industry.