Several Reactions Catalyzed By Palladium And Their Use In The Synthesis Of Pharmaceutical Intermediates

Because of the extensive applications,metal-catalyzed coupling reactions have drawn much attention from chemists and have been widely applied in the fields of chemistry,biology,pharmaceutical modification and material construction.The traditional homogeneous metal-catalyzed reactions suffer the difficulties in catalyst recovery,metal residues in products,expensive catalyst cost et.al.Therefore,our research group has developed a polyaniline-supported palladium catalyst.The strong coordination effects of nitrogen on the polymer supporter with metal restrain metal leakage and reduce the metal residues in products.As a heterogeneous catalyst,the polyaniline-supported palladium can be easily recycled and reused for many times.The catalyst has been successfully applied in the Heck reactions.On the other hand,investigations on C-H bond activation are unfolding recently.This technology can reduce waste generation,shorten the synthetic route,save the production cost and has significant industrial application value.We have conducted some explorations on C-H bond activation.Using alkenes as precursors,the palladium-catalyzed olefin functionalizations were achieved under mild conditions to construct C-C bond and C-hetero bond,which are more feasible and practical-The method avoids the use of directing groups.Cis-insertion occurred during the insertion of Pd-H species with C=C bond.This thesis reports the application of several palladium-cataly2zed reactions in the synthesis of pharmaceutical intermediates.The content is given as follows:1.The catalytic activity of the abundantly prepared and long-time stored polyaniline-supported palladium was investigated through the Suzuki and Sonogashira reaction.A large number of related derivatives were synthesized.The structure of the products are determined by NMR,temperament and IR data,and the highest yield reached 99%and 96%.It was found that the catalyst could be stored for quite a long time without deactivation.Besides,the technology has been applied in the modification of Lapatinib and Ethisterone intermediates.2.Pd catalyzed olefin hydrogen-arylation reactions were investigated.By means of adjusting the conditions of the reaction and determining the product structure and yield through Gas Chromatograph,it was shown that the reaction is more likely to go through the insertion of L*PdH to the olefin.Finally,the C-C bond is constructed one-step by the reaction of aryl halide with the palladium species.