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Atom Transfer Radical Processes: From Catalyst Design To Polymer Synthesis, Characterization, And Application, Michael Novak
Atom Transfer Radical Processes: From Catalyst Design To Polymer Synthesis, Characterization, And Application, Michael Novak
Electronic Theses and Dissertations
Due to the toxicity of heavy metals and their prevalence in the environment there exists a need to develop highly active transition metal catalysts ultimately reducing the amount needed for chemical transformations. Additionally, there is interest in the scientific community for creating new materials that can remove these pollutants from industrial wastewater prior to its release into the environment. The work presented here focuses on the reduction and removal of heavy metals from industrial hazardous waste by designing novel highly active catalysts and developing polymeric adsorbents.
Highly active catalyst complexes consisting of novel hybrid ligands, 2-(dimethylamino)ethyl-bis-[2-(pyridylmethyl)amine] (M1-T2), and bis[2-(dimethylamino)ethyl]-2-(pyridylmethyl)amine (M2-T1), …
Greening Of Catalytic Processes Using First-Row Transition Metals For Atom Transfer Radical Addition And Transfer Hydrogenation, Gabrielle Pros
Greening Of Catalytic Processes Using First-Row Transition Metals For Atom Transfer Radical Addition And Transfer Hydrogenation, Gabrielle Pros
Electronic Theses and Dissertations
This work focused on “greening” catalytic processes, atom transfer radical addition (ATRA), which adds an alkyl halide across and alkene, and transfer hydrogenation/dehydrogenation, which reduces a carbonyl without needing direct H2 gas. Part of “greening” of these processes is through using abundant first row metals, Cu and Ni for catalysis. One aim was to design new ligands which would be more active in these systems; the second was investigation of additives for catalyst regeneration to reduce the catalyst loading necessary for high yields.
The TPMA* family was investigated in ATRA. Rate constants followed the expected trend, which increased …
C-Metalated Nitriles: Diastereoselective Alkylations And Arylations, Robert John Mycka
C-Metalated Nitriles: Diastereoselective Alkylations And Arylations, Robert John Mycka
Electronic Theses and Dissertations
Development of an sp3 hybridized halogen-magnesium exchange route to Grignard reagents, chelation-controlled asymmetric induction of γ- and δ-hydroxynitriles as well as a diastereoselective arylation procedure for C-zincated nitriles have been explored. Sequential addition of i-PrMgCl and n-BuLi to 3- and 4-carbon iodoalcohols triggers a facile halogen-metal exchange to generate cyclic magnesium alkoxides capable of intercepting electrophiles to produce a diverse range of substituted alcohols. This work advances progress toward the synthesis of highly desirable chiral Grignard reagents.
Double deprotonation of γ- and δ-acyclic hydroxynitriles with i-PrMgCl effects highly diastereoselective alkylations via a singly-chelated magnesiated nitriles. …
Nontraditional Hydrogen Bonding In Asymmetric Lewis Acid Catalysis, Brandon Vernier
Nontraditional Hydrogen Bonding In Asymmetric Lewis Acid Catalysis, Brandon Vernier
Electronic Theses and Dissertations
In the field of asymmetric induction, there is a shift from the synthesis of reaction
specific chiral auxiliaries towards a broader mechanistic approach. Our approach is to
develop a theory of asymmetric catalyst design from first principles. The Diels-Alder
reaction of 2-methacrolein and 1,3-cyclopentadiene in the presence of 15 mole % lmenthoxy
aluminum dichloride, reported by Koga, achieved the (S)-exo-Diels-Alder
cycloadduct with 72% ee (0% ee Endo for acrolein). The dramatic change from 72% to 0%
ee is a significant fact that has been overlooked in practical organic synthesis.
In the first phase of this work, the conformational landscape of …