Study Of Ortho-Activation Of Aryl (Alkenyl) Halides Catalyzed By Palladium/Norbornene

Catellani reaction introduces the electrophilic reagent and the termination reagent into the C-I bond of aryl iodide by the synergistic catalysis of palladium and norbornene,and can flexibly introduce different functional groups into aryl iodide by the combination of different electrophilic reagents and termination reagents.This paper mainly focuses on the C-I bond ortho-esterylation and ipso-thioetheration of aryl/alkenyl iodide using palladium and norbornene as co-catalysts.(1)Research progress of Catellani reactionThis part mainly introduces the mechanism and development of Catellani reaction,and summarizes the related work of introducing different electrophiles into Catellani reaction,as well as the related work of introducing different functional groups into aryl borides,indoles and aromatics with inducer groups by the co-catalysis of palladium divalent catalyst and norbornene in recent years.(2)Study on ortho-esterylation/ipso-thioetheration of aryl iodide catalyzed by Palladium/norborneneThis part mainly introduces our work on introducing ester group and thiophenol part of thiocarbonate into C-I bond ortho-and ipso-position of aryl iodide through the synergistic catalysis of palladium and norbornene.The reaction has the advantages of mild reaction conditions,cheap and readily available raw materials,high atomic economy,wide application range of substrates and good chemical selectivity.A satisfactory yield of 68% was obtained in the gram test,which proves that the reaction has good application potential.In the derivatization of ortho-thiolated aryl esters,we successfully converted it into alcohol,acid,sulfoxide,sulfone and isothiazolone oxide compounds under mild conditions.(3)Study on ortho-esterylation/ipso-thioetheration of alkenyl iodide catalyzed by Palladium/norborneneThis part mainly introduces our work on C-I bond ortho-esterylation/ipsothioetheration of alkenyl iodide through the co-catalysis of palladium and norbornene.The synthesis of tetrasubstituted olefin is often faced with the challenge of regional selectivity control.However,we use alkenyl iodide as raw material,and use palladium and norbornene as co-catalysis to ensure the regional selectivity of orthoesterylation/ipso-thioetheration reaction.The reaction has the advantages of cheap raw materials and high atomic economy.The ester and thiophenol parts of raw thiocarbonate are introduced into the target molecule,and there is no waste of atoms.