Copper-catalyzed Borylation And Cyclization Of Cinnamyl Carbamoyl Chloride And The Multi-component Reaction Of Ketenimine Based On The CuAAC Pathway

The inexpensive copper-catalyzed borylation reaction has become an effective method for the synthesis of organoboron compounds due to its wide substrate applicability.This is not only an important source of the substrate molecular library of the Suzuki reaction,but also an important means for modifying the framework of organic molecules in the later stage.Because this method constructs C-C bonds at the same time as C-B bonds,C-B bonds can be transformed into a variety of functional groups,and the formation of C-C bonds provides a new method for the synthesis of various organic molecules.Through reasonable reaction design,we have realized the cyclization reaction of olefin borylation catalyzed by inexpensive copper metal,and carried out extensive and in-depth research on this basis.In addition,we have also studied the copper-catalyzed reaction of azides and alkynes,and carry out multi-component reaction research on this basis,in order to synthesize more organic intermediates with potential medicinal value.The content of this article consists of the following two aspects:1.Cinnamyl carbamoyl chloride is catalyzed by metal copper to generateγ-lactam compounds with potential protease inhibitory activity.We have proved the all-cis structure of the compound by X-single crystal diffraction of the product.The copper-catalyzed borylation reaction successfully realized the construction of nitrogen-containing heterocyclic rings,which provided a new idea for the synthesis of nitrogen heterocyclic compounds.Substrate expansion experiments show that the reaction has good yields and wide substrate applicability.At the same time,we transformed the product at a later stage,and successfully realized the synthesis of 2-aryl-3-hydroxy-γ-lactam Ⅱ-14 and 2-aryl-3-furyl-γ-lactam Ⅱ-15.2.The copper-catalyzed reaction of azides and alkynes(CuAAC)to form ketenimine often requires the activation of azides.We improved the substrates in total to achieve the CuAAC reaction of non-activated azides.The unstable ketenimine intermediate was obtained,and finally the multi-component reaction of the ketenimine was realized by the capture of the nucleophile benzylamine.Preliminary experimental explorations show that the reaction is due to the increase of the substrate benzimidazolyl electron-withdrawing ability to achieve unexpected conversion,synthesis of stable benzoguanidine compounds,such compounds have a wide range of applications in the fields of pesticide chemistry and materials.