Copper-catalyzed Oxidative Difunctionalization Of Alkenes Utilizing Trimethylsilyl Azide And Molecular Oxygen

Nitrogen-based structural motifs are important functionalities in organic synthesis,which can be reformed to a diversity of other advantageous functional groups,so aza introduction reactions are significant tools to access azides,nitriles,amines,amino acids,aminonitriles,aziridines,as well as triazoles,and have been widely used in natural products,organic pharmaceutical,pesticidal,dye,pigment,liquid crystal,and high polymer material industries.This thesis focuses on oxidative nitrogen insertion reactions,in which two catalytic oxidative methodologies are used to accomplish the addition of nitrogen and oxygen simultaneously.In synthetic chemistry,the highly selective catalytic transformation of organic compounds is of extreme importance.Dynamic catalysis includes the difunctionalization of double bond either the correspondinghomo-difunctionalizationorhetero-difunctionalization,the transformation of alkenes to aldehyde and nitriles via cleavage.In these strategies,catalytic oxidative systems can be difunctionalized the substrates radically.The first methodology is about difunctionalization of unactivated terminal olefins to ketoazides utilizing TMSN₃ as a nitrogen source and molecular oxygen as both an oxidant and oxygen source catalyzed by copper（II）triflate.Reaction conditions such as different types and amount of solvents,catalysts,nitrogen sources,temperature,and reaction time were optimized.Furthermore,electronic effects,substitution effects and steric effects of substrates on the reaction were evaluated in our research.Styrenes having mono,disubstitutions on aromatic rings,and fused ring all afforded corresponding ketoazidation products with regioselectivity.Some olefins responded to this catalytic system in completely different fashion.For instance,olefins in conjugation with aldehydes are transformed to nitriles rather than to ketoazidation products while extended conjugated substrate gave interesting cleavage pattern under the standard conditions.To get insight into the mechanism,various control experiments were also tested and the mechanism of this reaction was also proposed.This green methodology has wide substrate scope under mild reaction conditions and provides a useful tool for the synthesis of various difunctionalized products.The second oxidative catalytic system is capable to give two different functionalized products;aldehyde and nitrile from olefins under mild reaction conditions utilizing very extremely low organo-copper catalyst with TMSN₃ as a nitrogen source and molecular oxygen as both an oxidant and oxygen source.In this context,various parameters such as types and amount of solvents,catalysts,nitrogen sources,temperature,and reaction time were investigated in detail.The scope of this methodology is currently ongoing.Moreover,this methodology is the first example of utilizing transition metal organo-copper salt in which carbon-carbon double bond cleavage took place and one of resulted product is an aldehyde while another is nitrile representing oxygenation and nitrogenation respectively.