Pd-catelyzed C-H Functionalization For The Synthesis Of Planar Chiral Molecules And Aryl Ketones

This thesis mainly focused on four parts:the synthesis of planar chiral metallocene compounds,the progress of Catellani Reaction,the synthesis of diary]ketones and aryl alkyl ketones via Catellani Reaction.This paper can be divided to following four chapters:Chapter one:Palladium-Catalyzed Intramolecular Asymmetric C-H Functionalization Reaction of Planar Chiral Metallocenes.Great attentions have been arised since the planar chiral metallocenes were found in 1966.They can be used as planar chiral ligands or catalysts.We reported a methodology for the synthesis of planar chiral ferrocene analogues in an efficient way.This reaction via intramolecular C-H functionalization,asymmetric synthesis metallocenes compounds.It has the following advantages:1,The reaction is simple,and substrates can be easily obtained.2,this reaction uses catalysts and ligands,such as(R)or(S)-BINAP,was commerically available.Chapter two:The Progress of Catellani Reaction.This chapter mainly describes several termination methods of the Catellani Reaction,introduces some types of new electrophiles reagents which were developed in recent years.And it introduces the applications and the development of this type of reaction in total synthesis.Chapter three:The study on the synthesis of diary]ketones via Catellani reaction.Diaryl ketones have been found in many natural products.This chapter mainly concerns about the synthesis of diaryl ketones by using Catellani Reaction.And aryl acyl acid was used as electrophile reagent,and Heck Reaction was used as termination reaction.After optimizing the reaction condition,we found this reaction need stoichiometric equivalent water as additive.The kinetic study shows the real active acyl reagent probably is acid anhydride.X-ray chromatography analysis comfirmed the absolute configuration.The reaction has broad substrate scopes,the substrates are commercial available.Chapter four:the synthesis of aryl alkyl ketones via Catellani Reaction.Aryl alkyl ketones can be found in many natural products and drug intermediates.This chapter mainly concerns about using Catellani Reaction to synthesize aryl alkyl ketones.Mixed anhydrides are prepared as electrophile reagents,in order to study the influence of eletron donar groups or withdraw groups in the reaction.And 2,4,6-trichloride benzoyl chloride and alkyl acid are be used to prepare mixed ahhydrides,and use them as electriphile reagents in Catellani Reaction,making the preparation of aryl alkyl ketones come true.