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Synthesis Of N-containing Organic Compounds From Carbon-carbon Multiple Bonds

Posted on:2022-06-17Degree:DoctorType:Dissertation
Institution:UniversityCandidate:Arshad AliFull Text:PDF
GTID:1481306491455434Subject:Chemistry
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Nitrogen containing organic compounds is an important and unique class among the applied branches of organic chemistry,with a significant research dedicated to the development of novel compounds.These molecules have increasing attention over the past two decades and contributed to the development of numerous organic synthesis protocols and found abundant applications in the pharmaceuticals,materials science,as well as chemical industry.Alkenes and alkynes are abundant chemical raw materials,which can be easily obtained from either cracking of petroleum and coal or chemical synthesis in the lab.What’s more,these moieties are also broadly exsited in natural compounds.In this case,the incorporation of nitrogen source across the carbon-carbon multiple bonds makes make great sense for both academic and industry.In this thesis,we make a deep investigation on the synthesis of N-containing organic compounds from carbon-carbon multiple bonds.The main body of this thesis focus on the chemical transformation of alkynes into ketenimine intermediates or α-imine metal carbene intermediates and their further participation in cascade reaction,as well as the aminative difuntionalization of unactivated alkenes;both play an important role in the synthesis of N-containing compounds.In Chapter 1,we briefly summarized the chemistry of ketenimine and α-imine metal carbene intermediates and the aminative difunctionalization of unactivated alkenes,both of which provide efficient access to N-containing compounds.In Chapter 2,we described a novel and applicable preparation of 4-diazoisochroman-3-imines via Cu(I)-catalyzed cascade reaction of(2-ethynylphenyl)-methanols with sulfonyl azides.This method involved ketenimine intermediates,and the synthesized cyclical α-imidates could undergo reductive derivatizations to 4-methyl-N-(4-oxoisochroman-3-yl)benzene sulfonamide,4-methyl-N-((Z)-4-(2-(tetrahydrofuran-2-yl)hydrazono)isochroman-3-ylidene)benzenesulfonamide as well as the stable 1,2,3-triazoles.In Chapter 3,a Rh(II)-catalyzed transannulation of aldehyde-tethered N-sulfonyl triazoles with electron-rich aromatic nucleophiles is reported for the first time to afford functionalized 6-substituted piperidin-3-ones.This reaction has a broad substrate scope including both aliphatic and aromatic N-sulfonyl-1,2,3-triazoles together with various aromatic nucleophiles.In Chapter 4,a catalytic intermolecular diamination of unactivated alkenes with electron-rich amino sources has been discolosed.By employing a directing-group strategy,a copper-catalyzed diamination of unactivated alkenes was realized under neutral conditions.Symmetrical diamines were efficiently accessed in a highly diastereoselective manner with readily available dialkylamines as amino sources,while a one-pot,two-step operation was necessary to produce unsymmetrical diamines.These reactions were proposed to proceed through an aziridinium intermediate.
Keywords/Search Tags:Ketenimines, α-Imine metal carbenes, Aminative difunctionalization, Nitrogen-containing compounds, carbon-carbon multiple bonds
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