Transition-metal-catalyzed Cross-coupling Reaction With N-tosylhydrazones

In recent years,the transition-metal-catalyzed cross-coupling reaction with tosylhydrazones as coupling components has become a research area of focus,which has been widely applied to construction of C-C bonds,C-S bonds,and C-N bonds in the synthesis of natural products and pharmaceutically active molecules.The reaction mainly involves the processes of metal carbene formation and migratory insertion.Palladium-catalyzed allylation reaction with the release of nitrogen and copper-catalyzed benzylation of?-ketoester were studied.1.Pd-catalyzed allylation reaction between sulfonylhydrazones and aryl bromide with the release of nitrogen has been studied.The optimal reaction conditions were found after the scanning of bases,catalysts,ligands,and so on.The reaction proceeded efficiently in toluene at 80? with 5 mol%Pd?OAc?₂ as a catalyst,12.5 mol%L4 as a ligand,and Et₃N as a base.The yields of allylsulfones are up to 83%.2.A simple and efficient method for the benzylation of?-ketoesters has been studied.The optimal reaction conditions are found after the scanning of catalysts,bases,solvents and so on.The reaction proceeded efficiently in toluene at 60? with CuI as a catalyst and Cs₂CO₃ as a base.The yields of?-benzyl-?-ketoesters are up to 93%.