Mechanism Of AuBr₃Catalyzed Synthesis Of Highly Substituted Indolizine Based On2-Propargylpyridine And Study On The Nitrogen Nitrogen Bond Cleavage Of The Radical In Initiation

In the present paper, the density functional theory (DFT) is employed to study the reaction mechanism of AuBr3catalyzed synthesis of highly substituted Indolizine based on2-propargylpyridine. Additionally, we also developed a methodology for the ortho-amination of1-naphthols triggered by electron transfer. The dissertation could be described as the following two parts:1. Mechanism of AuBr3Catalyzed Synthesis of Highly Substituted Indolizine Based on2-PropargylpyridineThe calculated results show the N-atom in pyridine attacks on triple bond followed by two step proton transformation to form Au-carbene intermediate. Finally, the G (H, SiMe3, GeMe3) substituent group transfers to C2to form product. Furthermore, the GeMe3as the substituent group transfers to C2which is fairly easy. In addition, the theoretical research also illustrates that the reaction produces indolizine with equal distribution of deuterium between positions2-C and3-C (eql) under standard cycloisomerization condition. So far, this work has a significant guidance for understanding the type of reaction and designing new reaction.2. Study on the nitrogen nitrogen bond cleavage of the radical in initiationWith TEMPO (20mol%) as the catalyst,N-methyl-N-phenyl-hydrazine (2equiv.) as the amine source, the direct ortho-amination of1-naphthols could be easily achieved. The reaction was carried out at60℃under N2atmosphere. The procedure was simple, highly efficient. The possible mechanism was discussed, which may involve a radical-polar crossover reaction induced by electron transfer.