Cp*Ir(?)-Catalyzed C-H Activation Amination Reaction

In a variety of important C-N bond construction methods,starting from the direct C-H bond activation to form C-N bond is the most ideal method.This method can directly functionalize a hydrocarbon substrate without preinstallation of a reactive group,with green chemistry and atom economy requirements.This thesis firstly reviews the latest research progress of C-H amination reaction catalyzed by transition metal,based on different directing groups and transition metals.We found that the key to the application of C-N bond construction to organic synthesis is the diversification of directing groups and amine sources by comparing characteristics of the various amination reactions.Therefore,we choose a series of functionalized alkyl azides as amino resources and benzamides as the substrates.With the promotion of catalytic amount base(CsOAc),the orthor C-H amination of benzamides was achieved.Then,we selected benzamide with different substituents as the substrate and alkyl azides with ester group as nitrogen source.In the catalytic system of Cp*Ir(III)-CsOAc,the orthor C-H amination products were obtained with higher yield and selectivity.The method is also applicable to the late-stage derivatization of complex alkyl azides with biological activity and drug activity.In addition,based on our previous work about acyl azide as nitrogen source,we found that-OCH2CCI3 is a good leaving group in the molecular structure of TrocN3,the reaction activity could be promoted and the products could be further directly transformated.In order to extend this characteristic of TrocN3,we have attempted to catalyze the C(SP3)-H amination of TrocN3 with oxime ether as directing group under Ir(?)catalysis.It is found that TrocN3 can directly C(sp3)-H aminating with oxime ether in NaOAc promoted Ir(?)catalyst system.Various substrates containing inert C(sp3)-H bonds smoothly undergo this process with relative broad functional-group tolerance,mild conditions and high yield.We believe that this strategy represents an efficient route to oleanolic acid derivatives for natural products and medical studies.The amidated products not only can be directly deprotected to form primary alkyl amines,can also be transformated to carbamate and urea compounds.Meanwhile,we also achieved the late-stage modification of oleanolic acid derivatives with drug activity.