Study Of Iron Porphyrin Catalyzed Trapping Of Ammonium Ylides By Electrophiles

As the most abundant transition-metal,iron is cheap,safe and so on.The replace of noble metal catalysis by iron catalysis has become one of research focuses by synthetic chemists.Although the reaction of iron catalyzed decomposition of diazocompounds has not been discovered since 90s of last century,and there are few studies reported in this area.iron catalyzed decomposition of diazocompound still showed very good catalytic properties in some reactions,iron carbine can be formed by iron and diazocompunds,and then undergo a series of transformations,such as cyclopropanation reactions,insertion reactions etc.In previous reports,iron complex with spiro oxazoline ligand efficiently catalyzed asymmetric O-H insertions.At the same time,iron porphyrins showed very good selective N-H insertions.This paper focused on the study of the application of iron catalyst in the multicomponent reactions and the related mechanism investigation.The first chapter introduced iron carbene,multicomponent reactions based on trapping of ylide intermediates and zwitter ionic intermediates and application of ammonia in organic synthesis.At the same time,the research ideas of this paper are also introduced.The second chapter realized three component reaction of trapping ammonium ylides generated from aliphatic amines and diazocompounds for the first time.The reaction proved that the insertion of fatty amines through ylide process and provided efficient synthesis of ?-hydroxy ?-amino acid esters.The third chapter realized trapping of ammonium ylides generated from diazocompounds and ammonia by isatins,which provided method of synthesis of high value-added primary amine s using cheap raw materials ammonia.The process has a very good selectivity for the construction of primary amines.According to control experiments,we found that the steric effect of the product determines the chemoselectivity of the reaction.The fourth chapter of the thesis studied the mechanism of N-H insertion reaction and ylide trapping reaction.We have synthesized and characterized iron carbene with electron withdrawing group.And we realized the N-H reaction of iron carbene for the first time,proved that iron was formed in iron catalyzed N-H insertion reactions.The ylide trapping reaction of iron carbene was also accomplished,suggesting iron carbene was also the intermediate of three-component reaction.The fifth chapter of this paper studied metal-free halogenation of diazocompounds.The reaction realized efficient construction of 3-halooxoindoles.The process was genenal and we successfully realized the fluoride,chloride,bromide and iodide of diazoamides.We also implemented gram scale synthesis of 3-bromooxoindole.