Studies On Ni,Fe-Mediated Amidation Of Nitroarenes

Amides are not only important frameworks for peptides,proteins,and many natural products,but also important structures widely found in drugs,pesticides,and many biologically active molecules.More than 50%of the biologically active molecules contain amide moieties,and about 30%of the world’s highest-selling drugs or prescribed drugs bear amide functional groups,particularly a vast number of N-arylamide groups.Based on the importance of amides in the biological and pharmaceutical pesticide industries,the efficient development of amide synthesis has attracted much attention in organic synthesis.This thesis mainly studies the reaction of metal-mediated nitroarenes for the synthesis of N-arylamides.There are two sections:（1）direct amide synthesis via Ni-mediated aminocarbonylation of arylboronic acids and CO with nitroarenes.By using stable nitroarenes as aminating reagents,CO as carbonyl source,commercially available arylboronic acids,and abundant nickel metal powder（Ni）as both reductant and catalyst,the one pot reductive Ni-mediated aminocarbonylation of arylboronic acids and CO with nitroarenes was realized to access aryl amides.36 examples of amides with a yield of 46-92%were accessed,without homo-coupling products of arylboronic acids.This method can be applied in synthesis of several drug analogs,demonstrating potential application values.（2）Iron-mediated N-formylation reaction with nitroarenes and CO₂.By using readily available nitroarenes as aminating reagents,CO₂ as abundant carbonyl source,inexpensive iron as reductant reagent,and commercially available hydrosilane as activing reagent of CO₂,the direct N-formylation of nitroarenes and CO₂ was accessible.23 examples of N-aryl formamides were obtained in up to 85%yield.The merger of nitroarenes and CO₂for straightforward organic synthesis would provide a conceptual novel research basis for the utilization of CO₂ and convenient amide synthesis.