Studies On Palladium-catalyzed Tandem Reactions In The Construction Of C-C、C-X Bonds

Chapter IIn part one, Catellani reaction is a kind of typical cascade process involving multicomponent reaction in organic synthesis. The Catellani reaction provides an efficient approach of activating the ortho C–H bonds of aryl halides to offer dual functionalization products at both the ipso- and ortho-positions. The traditional Catellani reaction realized structurally complex polysubstituted aryl compounds by utilizing aryl halides, alkyl halides and terminal coupling reagents in the presence of palladium and norbornene. Here, we summarize that the developments and the latest research results of the Catellani-type reactions to date.In part two, norbornene is also one of the olefin compounds, which owning the typical nature of olefin. However, it is endowed with specificity because of the bridge ring skeleton. Here, we summarize the latest research progresses of norbornene which as the alkene in organic chemistry.In part three, the multifunctionalization of aryl compounds has emerged as an important chemical transformation in synthetic organic chemistry. The polyfluoroarene structure is important in natural products and complex pharmaceuticals. We here conclude that the latest research results of the multifunctionalization of aryl compounds and polyfluoroarene compounds. Chapter IIWe have realized a variety of synthetically useful bicyclic and tricyclic vinylarene products based on the typical Catellani reaction by using tosylhydrazones as the terminal coupling reagents. The process takes place via a key carbene migratory insertion and β-H elimination sequence. This modified Catellani-type reaction offers broad applications for developing various dual functionalizations of aryl halides. Chapter IIIDearomatization of arenes is widely utilized in the synthesis of complex biologically active natural products and pharmaceuticals. In addition, the spirocyclic compounds are unique structural units in many molecules. We have successfully obtained a serious of spirocyclic indolenine derivatives by utilizing aryl halides and indoles with tethered alkyl bromide as the substrates. This strategy firstly applied the Catellani reaction to an arylative dearomatization process. Chapter IVWe have developed a one pot to realize methylenecyclopentane derivatives by the ring opening of norbornene utilizing norbornene, aryl halides and tosylhydrazones as the substrates under mild conditions. The process takes place via cascade Heck-type coupling, carbene migratory insertion, C-C bond cleavage and β-H elimination sequence. In addition, the methylenecyclopentane subunits are obtained that are difficult to provide by traditional synthetic methods. Chapter VWe have efficiently synthesized sulfonyl substituted vinylarenes using halides substituted aryl halides as the substrates and using hydrazones as coupling substrates. The reaction involves a palladium carbene migratory insertion and sulfinate anion attacking arene as a nucleophile. Additionly, this stragy realized the best atom economy. Chapter VIBecause of the widely application in medicinal chemistry and functional materials science, polyfluoroarene structures are prominent structural motifs in organic chemistry. We have obtained various alkyl substituted polyfluoroarene derivatives via a cascade Heck/intermolecular C-H bond functionalization process. The initial materials are simple perfluoroarenes and aryl halides with tetherd alkyl which containing terminal double bond.