Palladium-catalyzed Oxidative Coupling Reaction

Transition metal-catalyzed oxidative coupling reaction have a very importantposition in organic synthesis, it is an effective method to build C–C, C–N C–O bond.In this dissertation, we first outline new developments of some common used solvents（THF, NEt₃, DMF, MeCN） as reactants in recent years, and further developmentthree synthesis methods of phenanthridinones, phenol and ketones.（1） Palladium-catalyzed selective Heck-type diarylation of allylic esters with arylhalides has been developed. Allylic esters are reacted with aryl iodides to provide thecorresponding1,3-diaryl propenes through a β-OAc elimination process. It isnoteworthy that the methodology can be applied in constructing the indole andbenzofuran skeletons.（2） A new, simple method for selectively synthesizing alkyl aryl ketones has beendeveloped by palladium-catalyzed oxidative coupling of trialkylamines with aryliodides. In the presence of PdCl₂（MeCN）₂, TBAB, and ZnO, a variety of aryl iodidesunderwent an oxidative coupling reaction with tertiary amines and water to afford thecorresponding alkyl aryl ketones in moderate to excellent yields. It is noteworthy thatthis method is the first example of using trialkylamines as the carbonyl sources forconstructing alkyl aryl ketone skeletons.（3） Synthesis of phenanthridinones via palladium-catalyzed oxidative coupling ofprimary benzamides with aryl iodides has been developed. This work allowsnon-OMe substituted primary benzamides reacted with aryl iodides to thecorresponding phenanthridinones through an N–H and dual C–H activation process. In general, an array of substituted primary benzamides proceeded well afforded productsin good yields.