| The transition metal-catalyzed activation of C-H bonds has gradually become the main method for functionalization of compounds.During the past decades,chemists have conducted a large number of C-H arylation,silylation reactions,alkylation reactions and alkenylation reactions catalyzed by Pd,Rh,Ru,Cu,and other metals Research,which provides a straightfoward access to modify the complex drug molecules and functional materials.Our group has been devoted to the research of phosphorous-directed C–H functionalization reactions,and have conducted numerous research on organic phosphine compounds,such as N-phosphorous protected indoles,diphenylphosphorbiphenyl,triphenylphosphine,and etc.A series of methodologies including arylation,silylation,boronation,alkenylation,and alkylation have been developed.All of these methods is of great significant for the in-situ modification of organic phosphine ligands,which can quickly construct an organic phosphine ligand library and improve the efficiency of rapid screening of new reactions.In my master thesis,the arylation and silylation of aniline and its derivatives has been studied in depth through the incorporation of NPtBu2 as directing group.Firstly,PCltBu2 was used to protect 3-methylaniline,under the catalysis of Rh（PPh3）3Cl,the arylation of aniline and bromobenzene has been developed employing Li OtBu as base,m-xylene as the solvent at 120 oC for 24 hours.The ortho position of aniline and its derivatives can be achieved.The reaction system is relatively mild and has good compatibility with various brominated aromatic hydrocarbons and aniline derivatives..In addition,the products obtained by this reaction are also a very important kind of ligands,which can be used in some specific reactions.Adding p-toluenesulfonic acid hydrate to the product’s tetrahydrofuran solution can remove the phosphine protecting group diagram to obtain aniline compounds,making the successtive conversion more abundant.The reaction system can also be applied to large-scale synthesis.Employing the same strategy,using[Rh（OAc）2]2 as the catalyst,hexamethyl disilane as the silicon source,and dioxane as the solvent,the ortho C–H bond silylation of anilines has been achieved at 125 oC for 48 hours.The system of this reaction is relatively simple and have a good tolerance to various derivatives of aniline.What’s more,it can also be applied to large-scale synthesis.The obtained silicon-based compounds as new silicon reagents have strong potential in various coupling reactions. |
