Investigation on Oxidative Allylation of Palladium Catalytic Reaction System

Author:Li Chun Sheng

Supervisor:jiang huan feng


Degree Year:2019





Alkenes are a class of important bulk chemicals in petrochemical and coal chemical industries.They have a wide range of applications in the national pillar industries such as medicine,materials,and daily chemicals,which greatly enriched material civilization of human.As an important material basis for the creation of new substances,how to efficiently convert and utilize alkenes has always been focused by chemists.Among them,the palladium-catalyzed selective and efficient synthesis of allyl-substituted compounds plays an important role in the efficient conversion of alkenes.There is no doubt that the Tsuji-Trost reaction represents the most classical allylic functionalization reactions.It is widely used in the synthesis of active bio-skeleton molecules and the development of pharmaceutical intermediates.In the past decade,the activation of allylic C-H bonds has undergone extensive research and significant progress has been achieved due to the high step and atom economy of the reaction.The palladium-catalyzed allylic C-H bond oxidation functionalization reactions have become another important means for the construction of carbon-carbon bonds and carbon-hetero bonds.Based on the backgrounds,this thesis reviewed the progress of palladium-catalyzed allylic carbon-hydrogen bonds functionalization reactions.Moreover,we investigated transformation of simple olefin with the high catalytic efficiency,high selectivity,high atom and step-economy.A series of new types of functional allylic substituted compounds were synthesized.The specific research contents are as follows:Chapter two described a palladium-catalyzed aerobic oxygenation of allylarenes with alcohols and phenols,which enabled the facile synthesis of(E)-allylether derivatives.With the utilzation of atmospheric pressure of oxygen as the green oxidant,in the presences of Pd(OAc)2,(E)-allylether derivatives were synthesized in high chemo-and regioselectivity.Moreover,this method featured high atom and step-economy.Chapter three described the palladium catalyzed selective aerobic oxidation of olefins with water,which efficiently constructed a series ofα,β-unsaturated aldehydes and allylic alcohol derivatives.The atmospheric pressure of oxygen was used as the green oxidant to achieve the regeneration of palladium catalyst.Through precisely controlling the reaction conditions,α,β-unsaturated aldehydes and allylic alcohol derivatives could be obtained.Chapter four described a straightforward method to construct a series of functionalized2-arylquinoline derivative had been reported.The present annulation process featured high functional-group tolerance and high atom economy,serving a valuable and practical method in synthetic and medicinal chemistry.Moreover,this transformation was supposed to proceed through oxidative of allylic C–H functionalization and cascade condensation/oxidative cyclization to form C=C and C=N bonds in one pot.Chapter five described a palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane to afford the corresponding homoallylic organoboronic esters with moderate to excellent yields was reported.This novel transformation provided an efficient strategy for the construction of homoallylic organoboronic esters in one-step with a broad substrate scope.This transformation was also characterized by the mild reaction conditions,simple operation and no need for the prefunctionalzation of alkene substrates.Chapter six described the first example of palladium-catalyzed allylic C-H oxidative allylation of sulfoxoium ylides to afford the corresponding conjugated dienones with moderate to excellent yields had been successfully developed.This reaction had the characteristics of high regioselectivity.This method also complemented Witting and Aldol strategies to access extended chalcone products,and broadened the applications of sulfoxonium ylides.Chapter seven described a protocol for the synthesis of allylic sulfides from simple allylic hydrocarbons with thiophenols derivatives via DDQ-mediated oxidative dehydrogenation strategy was described.This reaction possessed good functional group compatibility,broad substrate scope,and high atom-and step-economy.Moreover,the synthetic utility of this method could be highlighted by its application to the synthesis of versatile organo-sulfur compounds.