Synthesis Of Aromatic Ketone Derivatives Through Amine And Metal Compound Co-Catalyzed Alkyne-Carbonyl Metathesis

This paper mainly includes the following two parts: Part I: Application progress of metal catalysts in metathesis reactionsMetal plays an extremely important role in production and life,and metal compound catalysts make a great contribution to the chemical reactions.In the reaction of olefin metathesis,molybdenum or tungsten metal carbines were firstly explored as the catalysts in this field.Today,ruthenium metal carbine,especially the second generation of Grubbs catalyst,has played an important role in both industry and laboratory.In 2016,ferric chloride was disclosed as efficient catalyst in olefin-carbonyl metathesis,which achieved a significant breakthrough of the metal compound applied in this field.Iron is an earth-abundant and environmentally friendly metal,and the Fe(III)compounds are found to be an excellent catalyst in many reactions.Metal compound catalysts are also used in the reaction of alkyne-carbonyl metathesis for the synthesis of aromatic ketones.Aromatic ketones play an important role in both of medicine chemistry and material science,therefore,the development of new methods to construct these compounds is very meaningful.Part II: Studies on synthesis of aromatic ketones by alkyne-carbonyl metathesis catalyzed by amine and metal compoundThis part is mainly focused on the experimental studies.First,2,3-dimethoxybenzaldehyde and trimethylethylene were selected as the template substrates for intermolecular olefin-carbonyl metathesis.The optimum conditions of this reaction were established as using 20 mol% ferric chloride and carrying out the reaction at 40 °C in dichloromethane.However,under this optimized conditions,the substrate scope of this reaction is very limited.Subsequently,the intramolecular alkyne-carbonyl metathesis reaction was investigated by using(E)-2-methyl-3-(2-(phenyl-thynyl)phenyl)acrylaldehyde as the template substrate.The optimal conditions of this reaction include: p-toluenesulfonamide(5 mol%),iron trifluoromethanesulfonate(10 mol%),a temperature of 120 °C and 1,2-dichloroethane as the solvent.Under this conditions,the desired product can be obtained in 95% yield.A wide range of substrates was examined under the optimum conditions,and gave the corresponding products in good to excellent yields.The structures of the products were identified by nuclear magnetic resonance and high resolution mass spectrometry.