Palladium-Catalyzed β-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 achieveβ-funcationalized amides via C-H activation from simple amides,especially pivalamides.The following topics will be described in this thesis.（1）A reaction system ofβ-mesylation of primary sp³C-H bonds from amides has been established successfully.Amides can convert toβ-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）Theβ-funcationalized amides,such asβ-fluoroamides orβ-lactams,etc.can be produced easily fromβ-mesylated amide products through intermolecular or intramolecular S_N2 processes.（3）A reaction system ofβ-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 giveβ-arylated pivalamides with at 120^oC.These pivalamides including ^tBuCONH₂,^tBuCONHR and ^tBuCONR₂can undergo theβ-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.