The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln3+ ions have aroused great interest in lanthanide-catalyzed bond-forming reactions in aqueous media.
Several Ln3+-based Lewis acid precatalysts that were designed for Mukaiyama aldol reactions have been shown to be enantioselective, water-tolerant, and recoverable. Limiting the usefulness of these precatalysts are high ligand loadings and long reaction times that are necessary for high enantiomeric ratios. An understanding of water-coordination number, counter anion identitiy, solvent system, and ligand type effect(s) are necessary to improve upon existing Ln3+-based precatalysts.
I used luminescence-decay measurements and high performance liquid chromatography analyses to study the effects of water-coordination number, counter anion identitiy, and solvent system on reaction rates of Mukaiyama aldol reactions. I found that higher water-coordination numbers and higher water compositions gave rise to more reactive precatalysts for Mukaiyama aldol reactions that were catalyzed by Eu3+. I synthesized and characterized four new hexadentate ligands to study the effects of ligand type on reactivity and selectivity of Eu3+-based precatalysts for Mukaiyama aldol reactions. I used Eu3+ emission spectra and 1H-NMR experiments to study changes in Eu3+ coordination while titrating hexadentate ligands into solutions of Eu3+ and I found that Eu3+ is able to be coordinatively saturated in the presence of excess hexadentate ligands.
By studying Eu3+ in the presence of different anions and several chiral hexadentate ligands that contain ester, carboxylic acid, alcohol and amide donating groups I was able to find trends in reactivity and selectivity. In this thesis I describe the results that are likely to contribute to the development of highly reactive and selective Ln3+-based precatalysts.
","abstract_html":"<p>The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln<sup>3+</sup> ions have aroused great interest in lanthanide-catalyzed bond-forming reactions in aqueous media.</p> <p> Several Ln<sup>3+</sup>-based Lewis acid precatalysts that were designed for Mukaiyama aldol reactions have been shown to be enantioselective, water-tolerant, and recoverable. Limiting the usefulness of these precatalysts are high ligand loadings and long reaction times that are necessary for high enantiomeric ratios. An understanding of water-coordination number, counter anion identitiy, solvent system, and ligand type effect(s) are necessary to improve upon existing Ln<sup>3+</sup>-based precatalysts.</p> <p> I used luminescence-decay measurements and high performance liquid chromatography analyses to study the effects of water-coordination number, counter anion identitiy, and solvent system on reaction rates of Mukaiyama aldol reactions. I found that higher water-coordination numbers and higher water compositions gave rise to more reactive precatalysts for Mukaiyama aldol reactions that were catalyzed by Eu<sup>3+</sup>. I synthesized and characterized four new hexadentate ligands to study the effects of ligand type on reactivity and selectivity of Eu<sup>3+</sup>-based precatalysts for Mukaiyama aldol reactions. I used Eu<sup>3+</sup> emission spectra and <sup>1</sup>H-NMR experiments to study changes in Eu<sup>3+</sup> coordination while titrating hexadentate ligands into solutions of Eu<sup>3+</sup> and I found that Eu<sup>3+</sup> is able to be coordinatively saturated in the presence of excess hexadentate ligands. </p> <p>By studying Eu<sup>3+</sup> in the presence of different anions and several chiral hexadentate ligands that contain ester, carboxylic acid, alcohol and amide donating groups I was able to find trends in reactivity and selectivity. In this thesis I describe the results that are likely to contribute to the development of highly reactive and selective Ln<sup>3+</sup>-based precatalysts.</p>","abstract_has_math":false,"creators":["Averill, Derek James"],"institution":null,"degree_name":"Ph.D.","degree_level":"Open Access Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Matthew J. Allen"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-01-01T08:00:00Z","date_published":"2014-01-01T08:00:00Z","updated_at":"2026-07-24T05:59:56Z","subjects":["Aqueous","Asymmetric","Catalysis","Europium","Lanthanide","Mukaiyama","Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://digitalcommons.wayne.edu/oa_dissertations/1084","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Matthew J. Allen"]},{"key":"dc:creator","label":"Author","values":["Averill, Derek James"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2014-01-01T08:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Open Access Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Aqueous","Asymmetric","Catalysis","Europium","Lanthanide","Mukaiyama","Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://digitalcommons.wayne.edu/oa_dissertations/1084"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln3+ ions have aroused great interest in lanthanide-catalyzed bond-forming reactions in aqueous media.
Several Ln3+-based Lewis acid precatalysts that were designed for Mukaiyama aldol reactions have been shown to be enantioselective, water-tolerant, and recoverable. Limiting the usefulness of these precatalysts are high ligand loadings and long reaction times that are necessary for high enantiomeric ratios. An understanding of water-coordination number, counter anion identitiy, solvent system, and ligand type effect(s) are necessary to improve upon existing Ln3+-based precatalysts.
I used luminescence-decay measurements and high performance liquid chromatography analyses to study the effects of water-coordination number, counter anion identitiy, and solvent system on reaction rates of Mukaiyama aldol reactions. I found that higher water-coordination numbers and higher water compositions gave rise to more reactive precatalysts for Mukaiyama aldol reactions that were catalyzed by Eu3+. I synthesized and characterized four new hexadentate ligands to study the effects of ligand type on reactivity and selectivity of Eu3+-based precatalysts for Mukaiyama aldol reactions. I used Eu3+ emission spectra and 1H-NMR experiments to study changes in Eu3+ coordination while titrating hexadentate ligands into solutions of Eu3+ and I found that Eu3+ is able to be coordinatively saturated in the presence of excess hexadentate ligands.
By studying Eu3+ in the presence of different anions and several chiral hexadentate ligands that contain ester, carboxylic acid, alcohol and amide donating groups I was able to find trends in reactivity and selectivity. In this thesis I describe the results that are likely to contribute to the development of highly reactive and selective Ln3+-based precatalysts.
"]},{"key":"dc:title","label":"Title","values":["Lanthanide-Based Precatalysts For Carbon-Carbon Bond-Forming Reactions In Aqueous Media"]}]}],"canonical_facts":{"dc:contributor":["Matthew J. Allen"],"dc:creator":["Averill, Derek James"],"dc:date.available":["2014-01-01T08:00:00Z"],"dc:description.abstract":["The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln3+ ions have aroused great interest in lanthanide-catalyzed bond-forming reactions in aqueous media.
Several Ln3+-based Lewis acid precatalysts that were designed for Mukaiyama aldol reactions have been shown to be enantioselective, water-tolerant, and recoverable. Limiting the usefulness of these precatalysts are high ligand loadings and long reaction times that are necessary for high enantiomeric ratios. An understanding of water-coordination number, counter anion identitiy, solvent system, and ligand type effect(s) are necessary to improve upon existing Ln3+-based precatalysts.
I used luminescence-decay measurements and high performance liquid chromatography analyses to study the effects of water-coordination number, counter anion identitiy, and solvent system on reaction rates of Mukaiyama aldol reactions. I found that higher water-coordination numbers and higher water compositions gave rise to more reactive precatalysts for Mukaiyama aldol reactions that were catalyzed by Eu3+. I synthesized and characterized four new hexadentate ligands to study the effects of ligand type on reactivity and selectivity of Eu3+-based precatalysts for Mukaiyama aldol reactions. I used Eu3+ emission spectra and 1H-NMR experiments to study changes in Eu3+ coordination while titrating hexadentate ligands into solutions of Eu3+ and I found that Eu3+ is able to be coordinatively saturated in the presence of excess hexadentate ligands.
By studying Eu3+ in the presence of different anions and several chiral hexadentate ligands that contain ester, carboxylic acid, alcohol and amide donating groups I was able to find trends in reactivity and selectivity. In this thesis I describe the results that are likely to contribute to the development of highly reactive and selective Ln3+-based precatalysts.
"],"dc:identifier":["https://digitalcommons.wayne.edu/oa_dissertations/1084"],"dc:subject":["Aqueous","Asymmetric","Catalysis","Europium","Lanthanide","Mukaiyama","Chemistry"],"dc:title":["Lanthanide-Based Precatalysts For Carbon-Carbon Bond-Forming Reactions In Aqueous Media"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Open Access Dissertation"],"thesis:degree_name":["Ph.D."]},"updated_at":"2026-07-24T05:59:56Z"}