Studies On Synthesis Of Oxetane/Azetidine And C3-H Amination Of Quinoxalin-2(1H)-ones With Amines

The efficient and concise catalytic strategy is currently an important research direction of visible light catalysis.This thesis devises the C3-amination reaction,aza Paternò-Büchi reaction of quinoxalin-2(1H)-ones and the Paternò-Büchi reaction of naphthoquinone and indoles.This thesis includes the following four aspects:1.This chapter summarizes the common mechanism of aerobic oxidation driven by visible light,and expounds the classification of active oxygen and several oxidation methods in turn.At the same time,the mechanism and recent research of(aza)Paternò-Büchi reaction are summarized.2.In this chapter,the aza Paternò-Büchi reaction of quinoxalin-2(1H)-ones driven by visible light at room temperature was realized.The products of C3-amination reaction of quinoxalin-2(1H)-ones giving triplet energy lower than unmodified substrates.According to this conclusion,the aza-Paternò-Büchi reaction of 3-(1Hpyrazol-1-yl)quinoxalin-2(1H)-ones and various alkenes driven by visible light was realized.The mechanism study has shown that this reaction occurs through an energy transfer pathway.3.This chapter explored the Paternò-Büchi reaction of naphthoquinone and indoles for constructing oxetanes with high site selectivity.The stereochemistry of the products is controlled by a "sandwich" excited complex transition states formed by the?-stacking interaction between naphquinone and the electron-withdrawing indoles.4.The synthetic core of the key intermediate of Rosuvastatin Calcium is the construction and oxidation of the pyrimidine core.In this chapter,the Knoevenagel condensation and Michael addition reaction are used to efficiently construct the dihydropyrimidine that was oxidized to the pyrimidine through the green and efficient aerobic oxidation strategy driven by visible light.We optimized the synthesis route of Rosuvastatin Calcium intermediates and conducted gram-scale synthesis experiments.