Synthetic methodology for light-induced C-N bond forming reactions

This doctoral thesis mainly explores the chemical reactions between iminoiodinanes and unsaturated olefins under mild conditions. In the first part of the work, we used iminoiodinanes to react with silyl enol ethers under visible light irradiation. The α-hydrogen of the carbonyl group ofundergoes aza Rubottom reaction. Control experiments show the participation of the triplet nitrene diradical. Under mild conditions, we obtained α-amino ketone products in good yields. This reaction is applicable to iminoiodinanes with different substituents and has good tolerance to various halogens, electron-withdrawing, and electron-donating substituents. In addition, we also used this reaction in the C-H bond amination reaction of common natural molecules and drugs, such as menthone, and obtained good yields. Using the starting materials of optically pure enol ethers, we directed the formation of new C-N bond to obtain product. This derivatization reaction reflects the potential of triplet nitrenes in chemical production and drug synthesis. In the second part, we creatively used mild reaction conditions to obtain nitrene species at room temperature, and reacted the iminoiodinanes with the conjugated olefin in a [4+1] cycloaddition reaction to obtain the dihydropyrrole products , which represents the key heterocycle for the synthesis of renin inhibitors and vasodilators. The use of near-UV light can significantly improve the yield of the reaction. In addition, we also achieved related reactions of conjugated unsaturated olefin derivatives substituted with different positions and numbers of aromatic groups.