Rare-Earth-Metal-Catalyzed Synthesis Of Nitrogen-Containing Heterocyclic Compounds And Hydroboration Reductive Of Amides

In recent years,rare earth metal organic complexes have attracted widespread attention because of their unique catalytic properties.The catalytic reactions based on homoleptic bis?trimethylsilyl?amides of lanthanide metals have attracted great interest.Homoleptic bis?trimethylsilyl?amides of lanthanide metals have proved to be efficient catalysts for various organic transformations,due to their bifunctional catalytic properties bearing the strong Lewis acid of the lanthanide ion and the Br?nst base of the bis?trimethylsilyl?amido anion ligand.This dissertation has explored to some novel rare earth-catalyzed tandem reactions to construct heterocyclic nitrogen compounds and hydrogen transfer reduction reaction catalyzed by Ln[N?Si Me₃?₂]₃,main research achievements are shown as follows:1.Homoleptic bis?trimethylsilyl?amides of lanthanide metals could efficiently catalyze the cycloaddition reaction of alkynyl nitrile with secondary amine under mild conditions to form aminoisoindole.This reaction has significant advantages,such as mild reaction conditions,100%atomic efficiency and good functional group tolerance.Compared with the published synthesis methods of aminoisoindoles derivatives,the synthesis strategies involved in this paper can be compatible with aryl-substituted secondary amines.However,aromatic secondary amines have not been successfully transformed in the reported literatures.2.We report herein a rare-earth-metal-catalyzed insertion of a 2-pyridine C?sp²?-H bond into an intramolecular unactivated vinyl bond,it provides an important supplement for the synthesis of 4-azazindoles.This reaction include simple and mild reaction conditions,simple manipulation,high atomic efficiency,and wide substrate scope.This methodology is also used to construct other nitrogen-containing compounds such as naphthyridine derivatives.3.We have demonstrated that Ln[N?Si Me₃?₂]₃is an efficient catalyst for the hydroboration of amides.Also,this is also the first example of lanthanide-catalyzed hydroboration reduction of amides to amines.This reaction has significant advantages,such as excellent yields,good functional group tolerance,simple manipulation,it provides an important supplement for the reduction of amides to amines.