Studies On Transition Metal Mediated Reactions Of 3-Diazoindolin-2-imines

Diazo compounds are attractive substrates due to their ability to undergo diverse reactions to construct various structural motifs through C-C,C-O,C-N and C-P bond formations.Indole and its derivatives are important skeletons due to their presence in various natural products and important applications in dyes,pharmaceuticals,and pesticides.In this thesis,I have summarized the literature reported methods for the synthesis of various indole skeletons,reaction types of diazo compounds and my e:fforts to develop new methods for the synthesis of diverse indole derivatives by using various 3-diazoindolin-2-imines as carbene precursors.The results were summarized below:1.I have developed a method for the synthesis of azepino[2,3-b]indoles by the rhodium-catalyzed cycloadditions between 3-diazoindolin-2-imines and dienes.The reaction substrate has good universality,good regional selectivity,and the obtained structure has certain novelty.The reaction undergoes metal carbene intermediate,[2+1]cyclopropanation reaction and aza-Cope rearrangement process.In addition,when I treated 3-diazoindolin-2-imines with cyclic 1,3-butadienes,the corresponding[3+2]cycloaddition products were isolated.2.I have demonstrated a facile and efficient synthesis of 3-allyl-2-aminoindoles via the copper-catalyzed reaction of 3-diazoindolin-2-imines with allyltrimethylsilane.The operation is simple,the raw materials are easily available,and the obtained structure can be used for the synthesis of natural products.In addition,the reaction mechanism is relatively clear because I have obtained the reaction intermediate.Further,the obtained products could be further converted to 3-allyl-3-hydroxyindole-2-imines and 3-allyl-3-fluoroindole-2-imines.3.A method for the synthesis of 3-trifluoromethylthio-2-aminoindoles has been developed.The reaction mainly undergoes a copper trifluoromethylthiolate(in situ)in the presence of copper and silver trifluoromethylthiol,and then reacts with 3-diazoindolin-2-imines to synthesize 3-trifluoromethylthio-2-aminoindoles efficiently.Compared with the methods of introducing a trifluoromethylthio cation to the 3 position of indole in the literature,this method of introducing a trifluoromethylthio anion to the 3 position of indole has a certain novelty.