Palladium-Catalyzed Denitrative α-Arylation Of Ketones With Nitroarenes

As a commonly used synthetic building block,α-Arylated carbonyl compounds occupy an important position in organic synthesis,and they are widely present in numerous natural products,pharmaceuticals,agrochemicals,efficient ligands,organic materials,etc.Consequently,the development of highly efficient synthetic methodologies forα-arylation of carbonyl compound is of great significance to organic and medicinal chemists.Aryl iodides,aryl bromides,aryl chlorides,aryl triflates,and aryl arenesulfonates have been extensively used in palladium catalyzedα-arylation of carbonyl compounds.However,aryl bromides and iodides tend to be more expensive,aryl chlorides are less active,and aryl triflates and aryl arenesulfonates require prior synthesis and are less stable.The search for new aromatic sources is still important for modern arylation processes.In this dissertation,the palladium-catalyzedα-arylation of ketones with readily available nitroarenes and nitroheteroarenes provides access to usefulα-aryl andα-heteroaryl ketones is review.Thesis research mainly obtained the following results:1.The use of the Pd/BrettPhos catalysts was critical to achieve high efficiency for these transformations,whereas other catalysts led to decreased yields or no conversions.2.The intramolecular type substrate was also applied in this methodology and gave a chromone derivative.3.Polyaromatic carbonyl compounds can be easily obtained by multicomponent tandem reactions,via nucleophilic aromatic substitution(S_NAr)or cross-coupling reaction followed by this denitrative arylation.4.Kinetic experiments show that the electronic effect of nitrobenzenes has a greater effect on the reaction rate than the electronic effect of ketones.