Thesis advisor: Amir H. Hoveyda / Chapter 1. A Review of Sulfonate-Containing NHC Ligands in Copper-Catalyzed Enantioselective Transformations—Maneuvering Selectivities in Tight Space. A comprehensive review of enantioselective copper-catalyzed transformations, which are promoted by a chiral N-heterocyclic carbene metal complex that features a unique sulfonate motif, is provided in this chapter. Reactions have been categorized into four sets: allylic substitutions conjugate additions, Cu-B additions alkenes and multicomponent reactions. The mechanistic scenarios provided by DFT calculations accounts for their uniquely reaction profile in enantioselective allylic substitutions (EAS), enantioselective conjugate additions (EAS) and enantioselective Cu-B additions to alkenes. Mechanistic investigations (density functional theory calculations and deuterium labeling) point to a bridging function for an alkali metal cation connecting the sulfonate anion and a substrate’ s phosphate group to form the branched addition products as the dominant isomers via Cu(III) π -allyl intermediate complexes in EAS reactions. Sulfonate-bearing NHC ligand with different substitution patterns promote EAS reactions with different reactivity and enantioselectivity. We also developed a guideline to follow to choose the proper sulfonate-based NHC ligands according to the combination of the substrates and the nucleophiles. Chapter 2. NHC–Cu-Catalyzed Enantioselective Allylic Substitutions with Silyl-protected Propargyl Boron Reagent to Generate Tertiary and Quaternary Carbon Stereogenic Centers. Catalytic allylic substitution reactions involving a propargylic nucleophilic component are presented; reactions are facilitated by 5.0 mol % of a catalyst derived from a chiral N-heterocyclic carbene (NHC) and a copper chloride salt. A silyl-containing propargylic organoboron compound, easily prepared in multi-gram quantities, serves as the reagent. Aryl- and heteroaryl-substituted disubstituted alkenes within allylic phosphates and those with an alkyl or a silyl group can be used. Functional groups typically sensitive to hard nucleophilic reagents are tolerated, particularly in the additions to disubstituted alkenes. Reactions may be performed on the corresponding trisubstituted alkenes, affording quaternary carbon stereogenic centers. Incorporation of the propargylic group is generally favored (vs allenyl addition; 89:11 to >98:2 selectivity); 1,5-enynes can be isolated in 75−90% yield, 87:13 to >98:2 SN2′:SN2 (branched/linear) selectivity and 83:17−99:1 enantiomeric ratio. Utility is showcased by conversion of the alkynyl group to other useful functional units. Application to stereoselective synthesis of the acyclic portion of antifungal agent plakinic acid A, containing two remotely positioned stereogenic centers, by sequential use of two different NHC–Cu-catalyzed enantioselective allylic substitution (EAS) reactions further highlights utility. Chapter 3. NHC–Cu-Catalyzed Enantioselective Allylic Substitutions with Methylenediboron to Generate Tertiary and Quaternary Carbon Stereogenic Centers. A catalytic EAS method for the site- and enantioselective addition of commercially available di-B(pin)-methane to disubstituted allylic phosphates is introduced. Transformations are facilitated by a sulfonate-containing NHC–Cu complex and products are obtained in 63–95% yield, 88:12 to >98:2 SN2’/SN2 selectivity, and 85:15–99:1 enantiomeric ratio. The utility of the approach is highlighted by its application to the formal synthesis of the cytotoxic natural product rhopaloic acid A, in an all-catalytic-method synthesis route. Catalytic EAS methods of the di-B(pin) methane to Z-trisubstituted allylic phosphates are also disclosed and DFT calculations provide insights to the stereochemical models for those transformations and rationales for the choice of Z-trisubstituted allylic phosphates as the starting materials. Chapter 4. Enantioselective NHC–Cu-Catalyzed Prenyl Conjugate Additions to Enoates to Generate Tertiary Carbon Stereogenic Centers. An efficient catalytic protocol for generation of prenyl-bearing tertiary carbon stereogenic centers from aryl-substituted enoates was achieved in the presence of a chiral alkoxy-based NHC–Cu complex. A range of aryl and heteroaryl-substituted substrate were suitable substrates, the corresponding prenyl conjugate addition products were generated in up to 94% yield and 95:5 enantioselectivity. The utility of the current method has been shown in the application to the synthesis of a selective integrin antagonist. DFT calculations provided a stereochemical model for the ECA reaction employing alkoxy-containing NHC–Cu catalyst. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Copper is applied to many crops as a fungicide/bactericide, including plasticulture tomato growing operations. Field tests have shown that copper is sometimes found in ground water near these fields. Therefore, a laboratory study was undertaken to determine if this copper can result from plasticulture application and to determine the mechanisms that account for the movement through soil to the subsurface. From the factors that may affect this mobility process; TOC, dryness and its temperature cycle and water content of the soil were selected for study. These factors were investigated in both batch and continuous flow (column) processes. Copper mobility through soil columns was associated with TOC mobility, and soil drying had a major effect on both copper and TOC mobility. The concentration of copper eluted from columns containing dried soils was up to 20 times higher from those containing wet soils. The extent of dryness was found to affect mobility. First-flush-pattern for both copper and TOC from the columns was observed in all columns studies. In this research the copper mobility through the A- and B-horizon of Bojac sandy loam from the Eastern Shore of Virginia was studied. This study included both batch and column processes. The effects of pH, TOC and humic substances were investigated. The mobility of copper was found to be higher through A-horizon soil. The pH was found to have a considerable effect on the mobility of copper and TOC. The highest mobility of copper was achieved at pH 6.24 and its mobility through both soil horizons was associated with the mobility of TOC. A study of the humic substances indicated that fulvic acids had 4 times higher adsorption capacity for copper than humic acids. The association between fulvic acids and copper, coupled with the mobility of TOC and fulvic acids in the soil, accounted for transport of copper through soil columns. / Ph. D.

Controlled and selective electrochemical CO2 reduction to hydrocarbons and oxygenates utilizing energy from renewables such as solar energy is a promising alternative approach to store energy in chemical bonds while simultaneously close the anthropogenic carbon cycle, thus to address the twin problems of fossil fuels depletion and environmental challenges. Copper-based electrocatalysts have been demonstrated promising performance for CO2 reduction. However, Cu usually converts CO2 into a mixture, where more than 16 different species have been identified, and the selective yield of any product is limited by the competing reactions. Other major bottlenecks of Cu electrochemical catalyzed CO2 reduction reaction include the competition of hydrogen evolution reaction (HER), high overpotentials needed towards desired product, and lack of high-value products. In this dissertation, we addressed these three issues via surface modification, sulfurization, and coupling cathodic/anodic reactions, respectively. Specifically, (1) we developed a benzimidazole (BIMH)-modified copper foil catalyst, where the formed Cu(BIM)x complexes on Cu surfaces can enhance the Faradaic efficiency (FE) of C2/C3 products. The overall FE for CO2 reduction reaches 92.1% and the undesired hydrogen evolution reaction (HER) is lowered to 7% at -1.07 VRHE. (2) We demonstrated that Cu2S nanoarrays enable the selective CO2 reduction to formate starting at a very low overpotential (~ 120 mV), with high current density (over -20 mA/cm2 at -0.89 VRHE), and good Faradaic efficiency (>75%) over a broad potential window (-0.7 VRHE to -0.9 VRHE). Further- more, Cu2S catalysts show excellent durability without deactivation following more than 15 cycles (1h per cycle) of operation. The notable reactivity toward CO2 reduction to formate achieved by Cu2S nanoarrays may be ascribed to their ability to facilitate CO2 activation by stabilizing the CO2•− intermediate more effectively than pristine Cu foil. (3) We reported that direct electrochemical conversion of CO2 to 2-bromoethanol, a valuable pharmaceutical intermediate, is enabled by coupling the anodic and cathodic reactions with the presence of potassium bromide electrolyte in a membraneless electrochemical cell. The maximum Faradaic Efficiency of converting CO2 to 2-bromoethanol that we achieved is 40 % at -1.01 VRHE with its partial current density of -19 mA cm-2.

Historically, those communities or nations which are generously endowed with natural resources, and have the necessary skills to practice the liberal and useful art have become the most advanced civilizations. Furthermore, "of all the resources which are basic to civilization , the possession and utilization of minerals must be placed first." It would be difficult to estimate the over-all importance of the nonferrous metals industry (gold, silver, copper, lead, zinc) in helping America to become a great civilization. However. if it were possible, it would be considerable indeed. As Utah has been an important nonferrous mineral producing state for over 100 years, her contributions in helping America become a great civilization are unquestionable.

Aziridines and cyclopropanes are valued as important building blocks for the synthesis of a wide range of organic compounds, including biologically active compounds and pharmaceuticals. The development for more efficient and cost-effective catalysts for the atom transfer reaction with olefins is a continuing area of research in both organic and inorganic chemistry. Transition metal complexes, which catalyze reactions of olefins with nitrenes and carbenes, are well-developed efficient, approaches to the direct synthesis of aziridines and cyclopropanes, but traditionally rely on expensive synthetic methods. As part of our efforts in the catalytic formation of C—C and C—N bonds, herein we show the development of a new and efficient copper(II) catalysts that exhibits high reactivity forming cyclopropanes and aziridines from a range of olefins. These catalytic systems have also shown a propensity to conduct these atom-transfer reactions in aqueous solutions, affording the opportunity to use bio-macromolecules, like DNA, to induce enantioselectivity.

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