ingest cdrApp 2018-06-13T18:41:58.650Z 51cd2fe2-3fd7-401f-a923-a97bc3db68a2 modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T19:53:19.865Z Setting exclusive relation addDatastream MD_TECHNICAL fedoraAdmin 2018-06-13T19:53:31.378Z Adding technical metadata derived by FITS addDatastream MD_FULL_TEXT fedoraAdmin 2018-06-13T19:53:48.539Z Adding full text metadata extracted by Apache Tika modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T19:54:10.685Z Setting exclusive relation modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-11T15:10:47.174Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-18T10:48:03.787Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-08-21T19:35:59.089Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-09-27T20:25:38.445Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-12T10:55:15.729Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-17T16:13:46.463Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2019-03-21T21:12:13.467Z Kaila Margrey Author Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Spring 2018 2018 Organic chemistry Amination, Catalysis, C–H Functionalzation, Photoredox eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text Kaila Margrey Author Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Spring 2018 2018 Organic chemistry Amination, Catalysis, C–H Functionalzation, Photoredox eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text Kaila Margrey Author Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Spring 2018 2018 Organic chemistry Amination, Catalysis, C–H Functionalzation, Photoredox eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text Kaila Margrey Author Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Spring 2018 2018 Organic chemistry Amination, Catalysis, C–H Functionalzation, Photoredox eng Doctor of Philosophy Dissertation Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Kaila Margrey Creator Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Organic chemistry Amination; Catalysis; C–H Functionalzation; Photoredox eng Doctor of Philosophy Dissertation Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution 2018 2018-05 Kaila Margrey Author Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Spring 2018 2018 Organic chemistry Amination, Catalysis, C–H Functionalzation, Photoredox eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text Kaila Margrey Author Department of Chemistry College of Arts and Sciences Development of Aromatic and Aliphatic C–H Functionalizations via Photoredox Catalysis Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. Spring 2018 2018 Organic chemistry Amination, Catalysis, C–H Functionalzation, Photoredox eng Doctor of Philosophy Dissertation Chemistry David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Kaila Margrey Creator Department of Chemistry College of Arts and Sciences Carbon–hydrogen (C–H) bonds are ubiquitous in organic compounds, and the ability to functionalize C–H bonds selectively is a powerful strategy for late-stage derivatizations. The direct C–H functionalization of electron-rich arenes with azole coupling partners was demonstrated using an acridinium photoredox catalyst and a nitroxyl radical cocatalyst under an aerobic atmosphere, occurring via the intermediacy of an arene cation radical. High levels of site selectivity were observed with this methodology, and it proved applicable to a wide variety of arene and azole coupling partners, including complex bioactive molecules. Anilines could be constructed using ammonium carbamate as the nucleophilic coupling partner. The ability to predict the site of C–H functionalization on complex arenes is nontrivial, and for this reason, a predictive model was developed. This enabled the extension of our aryl amination to a wide variety of heterocyclic arenes that are common motifs in pharmaceuticals. Using electron density calculations, we could predict the major site of functionalization for over 60 arene substrates. We sought to extend this arene functionalization methodology toward aliphatic amine coupling partners. We demonstrated this capability with a wide variety of amino acid and primary amine coupling partners with arene substrates. Site selectivity was dependent on sterics of the arene, unlike our previous work with azoles. We also disclose the functionalization of arenes that cannot be oxidized by the acridinium catalyst, such as benzene and toluene, supporting a reactive amine cation radical intermediate. A modular functionalization of unactivated aliphatic C–H bonds was developed utilizing an acridinium photoredox catalyst, phosphate base, and several diverse radical traps. The development of a C–H azidation reaction highlighted good site selectivity on alkanes for tertiary functionalization exclusively. Through modifications of this system, a C–H diversification allowed for the formation of C–F, C–Br, C–Cl, C–SCF3, and C–C bonds. 2018-05 2018 Organic chemistry Amination; Catalysis; C–H Functionalzation; Photoredox eng Doctor of Philosophy Dissertation David Nicewicz Thesis advisor Erik Alexanian Thesis advisor Simon Meek Thesis advisor Michel Gagne Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Margrey_unc_0153D_17808.pdf uuid:b45c467d-8b1f-4915-b234-885b1272ce0a 2020-06-13T00:00:00 2018-04-26T18:28:34Z proquest application/pdf 43290945