Study On New Strategies For The Synthesis Of Organophosphine Compounds Catalyzed By Palladium Or Copper

Organophosphine compounds are one of the most important functional molecules,their unique chemical properties and biological activities make them widely used in life sciences,medicinal chemistry,material molecules and agricultural production.Therefore,the development of simple and efficient strategies to synthesize organophosphine compounds has attracted great attention in recent years.This thesis mainly summarizes the indole-type Catellani reaction catalyzed by palladium/norbornene and a new method for the synthesis of organophosphine compounds developed by me using this strategy during my Ph.D.study.In addition,this thesis also conducts a systematically study on copper-catalyzed phosphine-oxygen(P=O)-directed C-H arylation.The details includes the following five chapters:Chapter One:This chapter introduces the discovery process of Catellani reaction catalyzed by palladium/norbornene(Pd/NBE),and on this basis,briefly summarizes the current development of this reaction.After that,we focus on the indole-type catellani reaction in detail.Chapter Two:In this chapter,a palladium-catalyzed Catellani-type reaction of indole with diethyl(iodomethyl)phosphonate has been introduced.This new protocol provides an efficient and concise route to 2-methylene phosphonate indoles,which are key synthons for the construction of indole alkaloids.Besides,we also explored the electronic effect of the reaction through a large number of examples.Chapter Three:This chapter first briefly expounds the significance of developing phosphine oxygen(P=O)directing groups to participate in the activation of C-H bond catalyzed by transition metals,and on this basis,summarizes the functionalization of this kind of reaction.Among them,we elaborated the substrate selection and catalytic mode of the arylation reaction in detail.Chapter Four:This chapter introduces the regioselective arylation of the polycyclic aromatic hydrocarbons(PAHs)by using P=O directing groups catalyzed by cheap metal copper.On this basis,we also synthesized a series of arylated polycyclic compounds with potential fluorescence,and tested their fluorescence properties.Chapter Five:The ability to manipulate the site selectivity in C-H bond functionalization reactions is very important.This chapter introduces a new reaction strategy for the regioselective arylation of indoles at the C2 or C3 positions,achieved by adjusting the solvent(THF or Toluene)and with P(O)^tBu₂ as an auxiliary group.The control experimental results and density functional theory(DFT)calculations confirmed that Cu(III)dominated the formation of the C3-arylation products,and the acid produced in this process initiated the migration of C3-aryl group to the C2 site.Based on this methodology,some indole-based fluorescent molecules containing P(O)^tBu₂functional groups synthesized by us,and these molecules exhibit good optical properties.