Palladium-Catalyzed Synthesis Of Amides Via Organosilanes By Oxidative Carbonylation

Transition metal-catalyzed oxidative carbonylation has attracted extensive attention from chemists due to its high reaction efficiency,mild reaction conditions,broad functional group compatibility,and good regioselectivity.In this thesis,the research status of oxidative carbonylation under transition metal catalysis and the coupling reaction involving organosilicon reagents are reviewed.Then,a series of secondary amide and tertiary amide compounds were constructed by using carbon monoxide as a carbonyl source and oxidative carbonylation of aryl silane and aromatic amine under 1 atm.The optimal conditions including catalyst,additive,solvent,reaction temperature and carbonyl source were screened out,and the relationship between the reaction properties and the structure of the reaction substrate was investigated.Finally,CO was used as the carbonyl source,Pd?PPh₃?₂Cl₂?10 mol%?was used as the catalyst,copper?II?fluoride?2.0equiv.?was used as the additive,and acetonitrile?3.0 mL?was used as the solvent to react at 80°C for 24 h to obtain 37 kinds of amide compounds in a yield of 63%to 92%.The reaction conditions in this system are very mild and do not need the protection of inert gas.It is worth mentioning that the additive copper difluoride plays an indispensable role in the reaction,both as an activator to activate the carbon-silicon bond of the aryl silane,and as an oxidant to oxidize the Pd?0?to Pd?II?continues to participate in the reaction,effectively promoting the occurrence of amino acid acylation of the silicone reagent.The proposed method not only further enriches the synthesis route of amide compounds,but also opens the door for the application of organosilicon reagents in oxidative carbonylation conversion.