Copper-Catalyzed Aminoxylation Of Unactivated Alkyl C(sp~3)-H Bond With TEMPO To Synthesize N-Alkoxyamine Derivatives

N-Alkoxyamines are widely recognized as a kind of polyfunctional compound.They are effective initiators in the controlled radical polymerization especially in Nitroxide Mediated Living Radical Polymerizations.They provide powerful methods for controlling the polydispersity and molecular weight of growing polymer chains and offering access to complex polymer architecture.In addition,N-alkoxyamines are also applied as chiral building blocks,fireproofing agents,light stabilizers,rheology modifiers,as well as valuable precursors especially in biologically active natural products and pharmaceutical agents.And they can also contribute to self-healing polymer synthesis and theranostics.Hence,there has been an ongoing interest in developing simple,selective,scalable and cost-efficient methods for synthesizing functionalized N-alkoxyamines.This thesis mainly focused on copper-catalyzed aminoxylation of unactivated sp3 C-H bond with TEMPO to synthesize N-alkoxyamine derivatives.Based on rational experiments and optimization of conditions,we used ethyl benzene as a model substrate and TEMPO for optimizing conditions.We developed a mind and concise?Bpy?Cu^II?0.5 mol%?/TBHP catalyst system for the synthesis of N-alkoxyamines using TEMPO with different types of hydrocarbons.This catalyst system shows excellent reactivity and broad scope of substrates,including ketones,esters,nitriles,toluene,ethylbenzene,heterocycles,cyclohexene and cyclohexanes.Under the standard conditions,they generally furnished the desired N-alkoxyamine products in good to high yields.In addition,considering the importance of nitriles in organic synthesis and avoiding the use of highly toxic cynides.We discovered a novel copper-catalyzed cyanation of aryl iodides by activation of the C-CN bond of inert acetonitrile with TEMPO as an oxidant.We used1-iodonaphthalene as a model substrate,the acetonitrile as cyano source,cheaper Cu as the metal catalyst,bpy as the ligand and TEMPO as the oxidant to provide an amenable way for the preparation of aromatic cyanides in high yields successfully.