{"id":{"repo_id":"utswmed","oai_identifier":"oai:utswmed-ir.tdl.org:2152.5/10811"},"canonical_url":"https://search.dev.ndltd.org/etd/utswmed/oai:utswmed-ir.tdl.org:2152.5/10811","repository":{"repo_id":"utswmed","name":"University of Texas Southwestern Medical Center","base_url":"https://utswmed-ir.tdl.org/server/oai/request"},"display":{"title":"The Development of New Stereoselective Transformations Using Alkenyl Boronate Complexes","abstract":"Anionic, tetravalent alkenyl boron-"ate" complexes have emerged as powerful reagents for the stereoselective synthesis of chiral boronic esters via multicomponent coupling. These complexes can react with electrophiles through a 1,2-metalate rearrangement process, resulting in the net addition of a carbon-based migrating group and the electrophile across the alkene. While great advances have been made in the last decade, the synthetic potential of alkenyl boronate complexes has not yet been fully realized. This thesis will detail our efforts to develop new stereoselective reactions using alkenyl boronate complex nucleophiles. First, the evolution of alkenyl boronate complexes and their applications will be discussed. These reagents initially found heavy use in stereoselective olefin synthesis before being applied to multicomponent coupling reactions. In this vein, alkenyl boronate complexes have been shown to react with electrophiles of varying complexity in both polar and radical type mechanisms. Asymmetric catalysis has enabled access to enantioenriched organoboron compounds. The second chapter will describe our studies on the reaction between alkenyl boronate complexes and activated nitrogen heterocycles. Isoquinolines and quinolines react with alkenyl boronates to furnish alkylated, dearomatized heterocycles in a highly stereoselective manner. Details regarding the reaction mechanism and applications of the reaction products are shown. The third chapter will detail our investigations into enantioselective amination of alkenyl boronate complexes. Our strategy involves metal-catalyzed asymmetric aziridination of the alkenyl boronate complex, followed by stereospecific 1,2-migration and opening of the strained ring. Optimization experiments were conducted with chiral copper, rhodium, and iridium complexes with a focus on achieving good yield and enantioselectivity. Lastly, the fourth chapter will briefly discuss our initial efforts into achieving stereoselective alkenyl boronate complex functionalization using auxiliary-derived boronic esters. Similar boronic esters have been successful in asymmetric reactions such as allylations and homologations. We have shown that boronic esters containing C2 symmetrical diol ligands reliably form alkenyl boronate complexes and can react with activated isoquinolines with modest stereoselectivity. Initial results for a stereoselective epoxidation/ring opening strategy are also shown.","abstract_html":"Anionic, tetravalent alkenyl boron-"ate" complexes have emerged as powerful reagents for the stereoselective synthesis of chiral boronic esters via multicomponent coupling. These complexes can react with electrophiles through a 1,2-metalate rearrangement process, resulting in the net addition of a carbon-based migrating group and the electrophile across the alkene. While great advances have been made in the last decade, the synthetic potential of alkenyl boronate complexes has not yet been fully realized. This thesis will detail our efforts to develop new stereoselective reactions using alkenyl boronate complex nucleophiles. First, the evolution of alkenyl boronate complexes and their applications will be discussed. These reagents initially found heavy use in stereoselective olefin synthesis before being applied to multicomponent coupling reactions. In this vein, alkenyl boronate complexes have been shown to react with electrophiles of varying complexity in both polar and radical type mechanisms. Asymmetric catalysis has enabled access to enantioenriched organoboron compounds. The second chapter will describe our studies on the reaction between alkenyl boronate complexes and activated nitrogen heterocycles. Isoquinolines and quinolines react with alkenyl boronates to furnish alkylated, dearomatized heterocycles in a highly stereoselective manner. Details regarding the reaction mechanism and applications of the reaction products are shown. The third chapter will detail our investigations into enantioselective amination of alkenyl boronate complexes. Our strategy involves metal-catalyzed asymmetric aziridination of the alkenyl boronate complex, followed by stereospecific 1,2-migration and opening of the strained ring. Optimization experiments were conducted with chiral copper, rhodium, and iridium complexes with a focus on achieving good yield and enantioselectivity. Lastly, the fourth chapter will briefly discuss our initial efforts into achieving stereoselective alkenyl boronate complex functionalization using auxiliary-derived boronic esters. Similar boronic esters have been successful in asymmetric reactions such as allylations and homologations. We have shown that boronic esters containing C2 symmetrical diol ligands reliably form alkenyl boronate complexes and can react with activated isoquinolines with modest stereoselectivity. Initial results for a stereoselective epoxidation/ring opening strategy are also shown.","abstract_has_math":false,"creators":["McGettigan, James Edward, Jr."],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Tambar, Uttam","Ready, Joseph M.","Smith, Myles W","Qin, Tian"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2026,"date_issued":"2026-06-15T19:42:54Z","date_published":"2026-06-15T19:42:54Z","updated_at":"2026-07-24T05:52:22Z","subjects":["Alkenes","Boronic Acids","Catalysis","Stereoisomerism"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["1596185281"],"render_values":[{"text":"1596185281","href":null,"code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/2152.5/10811","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Tambar, Uttam","Ready, Joseph M.","Smith, Myles W","Qin, Tian"]},{"key":"dc:creator","label":"Author","values":["McGettigan, James Edward, Jr."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2026-06-15T19:42:54Z","2024-05","May 2024"]},{"key":"dc:type","label":"Dc Type","values":["Thesis","text"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Alkenes","Boronic Acids","Catalysis","Stereoisomerism"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2152.5/10811","1596185281"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Anionic, tetravalent alkenyl boron-"ate" complexes have emerged as powerful reagents for the stereoselective synthesis of chiral boronic esters via multicomponent coupling. These complexes can react with electrophiles through a 1,2-metalate rearrangement process, resulting in the net addition of a carbon-based migrating group and the electrophile across the alkene. While great advances have been made in the last decade, the synthetic potential of alkenyl boronate complexes has not yet been fully realized. This thesis will detail our efforts to develop new stereoselective reactions using alkenyl boronate complex nucleophiles. First, the evolution of alkenyl boronate complexes and their applications will be discussed. These reagents initially found heavy use in stereoselective olefin synthesis before being applied to multicomponent coupling reactions. In this vein, alkenyl boronate complexes have been shown to react with electrophiles of varying complexity in both polar and radical type mechanisms. Asymmetric catalysis has enabled access to enantioenriched organoboron compounds. The second chapter will describe our studies on the reaction between alkenyl boronate complexes and activated nitrogen heterocycles. Isoquinolines and quinolines react with alkenyl boronates to furnish alkylated, dearomatized heterocycles in a highly stereoselective manner. Details regarding the reaction mechanism and applications of the reaction products are shown. The third chapter will detail our investigations into enantioselective amination of alkenyl boronate complexes. Our strategy involves metal-catalyzed asymmetric aziridination of the alkenyl boronate complex, followed by stereospecific 1,2-migration and opening of the strained ring. Optimization experiments were conducted with chiral copper, rhodium, and iridium complexes with a focus on achieving good yield and enantioselectivity. Lastly, the fourth chapter will briefly discuss our initial efforts into achieving stereoselective alkenyl boronate complex functionalization using auxiliary-derived boronic esters. Similar boronic esters have been successful in asymmetric reactions such as allylations and homologations. We have shown that boronic esters containing C2 symmetrical diol ligands reliably form alkenyl boronate complexes and can react with activated isoquinolines with modest stereoselectivity. Initial results for a stereoselective epoxidation/ring opening strategy are also shown."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The Development of New Stereoselective Transformations Using Alkenyl Boronate Complexes"]}]}],"canonical_facts":{"dc:contributor":["Tambar, Uttam","Ready, Joseph M.","Smith, Myles W","Qin, Tian"],"dc:creator":["McGettigan, James Edward, Jr."],"dc:date":["2026-06-15T19:42:54Z","2024-05","May 2024"],"dc:description":["Anionic, tetravalent alkenyl boron-"ate" complexes have emerged as powerful reagents for the stereoselective synthesis of chiral boronic esters via multicomponent coupling. These complexes can react with electrophiles through a 1,2-metalate rearrangement process, resulting in the net addition of a carbon-based migrating group and the electrophile across the alkene. While great advances have been made in the last decade, the synthetic potential of alkenyl boronate complexes has not yet been fully realized. This thesis will detail our efforts to develop new stereoselective reactions using alkenyl boronate complex nucleophiles. First, the evolution of alkenyl boronate complexes and their applications will be discussed. These reagents initially found heavy use in stereoselective olefin synthesis before being applied to multicomponent coupling reactions. In this vein, alkenyl boronate complexes have been shown to react with electrophiles of varying complexity in both polar and radical type mechanisms. Asymmetric catalysis has enabled access to enantioenriched organoboron compounds. The second chapter will describe our studies on the reaction between alkenyl boronate complexes and activated nitrogen heterocycles. Isoquinolines and quinolines react with alkenyl boronates to furnish alkylated, dearomatized heterocycles in a highly stereoselective manner. Details regarding the reaction mechanism and applications of the reaction products are shown. The third chapter will detail our investigations into enantioselective amination of alkenyl boronate complexes. Our strategy involves metal-catalyzed asymmetric aziridination of the alkenyl boronate complex, followed by stereospecific 1,2-migration and opening of the strained ring. Optimization experiments were conducted with chiral copper, rhodium, and iridium complexes with a focus on achieving good yield and enantioselectivity. Lastly, the fourth chapter will briefly discuss our initial efforts into achieving stereoselective alkenyl boronate complex functionalization using auxiliary-derived boronic esters. Similar boronic esters have been successful in asymmetric reactions such as allylations and homologations. We have shown that boronic esters containing C2 symmetrical diol ligands reliably form alkenyl boronate complexes and can react with activated isoquinolines with modest stereoselectivity. Initial results for a stereoselective epoxidation/ring opening strategy are also shown."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2152.5/10811","1596185281"],"dc:language":["en"],"dc:subject":["Alkenes","Boronic Acids","Catalysis","Stereoisomerism"],"dc:title":["The Development of New Stereoselective Transformations Using Alkenyl Boronate Complexes"],"dc:type":["Thesis","text"]},"updated_at":"2026-07-24T05:52:22Z"}