Palladium-Catalyzed ?-Funcationalization Of Simple Amide Via Primary Sp~3C-H Activation

Primary sp³C-H bonds of simple amides is inert under common reaction conditions.In our study,we tried to achieve?-funcationalized amides via C-H activation from simple amides,especially pivalamides.The following topics will be described in this thesis.?1?A reaction system of?-mesylation of primary sp³C-H bonds from amides has been established successfully.Amides can convert to?-mesylation amides in the presence of methanesulfonic anhydride?Ms₂O?,Pd?OAc?₂?catalyst?,K₂S₂O₈?oxidant?,CF₃CH₂OH?solvent?at 80°C.Several amide substrates,such as N-monosubstituted linear,branch,cyclic alkanes,or electron-deficient benzyl compounds,are available in the reactions.?2?The?-funcationalized amides,such as?-fluoroamides or?-lactams,etc.can be produced easily from?-mesylated amide products through intermolecular or intramolecular S_N2 processes.?3?A reaction system of?-arylation from primary sp³C-H bonds on pivalamides has been established successfully.Pivalamides reacted with aryl iodides in the presence of AgTFA?CF₃CO₂Ag?,Pd?OAc?₂?catalyst?/CF₃CH₂OH?solvent?to give?-arylated pivalamides with at 120^oC.These pivalamides including ^tBuCONH₂,^tBuCONHR and ^tBuCONR₂can undergo the?-arylations smoothly to be arylated in moderate to good yields.Various aryl iodides,including either electron-rich or electron-deficient substituted groups are compatible in the coupling reactions.