ingest cdrApp 2018-06-13T17:50:35.716Z 51cd2fe2-3fd7-401f-a923-a97bc3db68a2 modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T18:35:48.516Z Setting exclusive relation addDatastream MD_TECHNICAL fedoraAdmin 2018-06-13T18:35:59.915Z Adding technical metadata derived by FITS addDatastream MD_FULL_TEXT fedoraAdmin 2018-06-13T18:36:26.693Z Adding full text metadata extracted by Apache Tika modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T18:36:38.491Z Setting exclusive relation modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-11T17:57:50.611Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-18T13:19:35.836Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-08-21T22:11:13.386Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-09-28T13:28:43.806Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-12T13:30:06.327Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-17T18:50:05.524Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2019-03-22T16:40:38.710Z William Czaplyski Author Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Spring 2018 2018 Organic chemistry C–H Functionalization, Photoredox, Polyolefin, Radical, Xanthate eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text William Czaplyski Author Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Spring 2018 2018 Organic chemistry C–H Functionalization, Photoredox, Polyolefin, Radical, Xanthate eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text William Czaplyski Author Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Spring 2018 2018 Organic chemistry C–H Functionalization, Photoredox, Polyolefin, Radical, Xanthate eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text William Czaplyski Author Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Spring 2018 2018 Organic chemistry C–H Functionalization, Photoredox, Polyolefin, Radical, Xanthate eng Doctor of Philosophy Dissertation Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution William Czaplyski Creator Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Organic chemistry C–H Functionalization; Photoredox; Polyolefin; Radical; Xanthate eng Doctor of Philosophy Dissertation Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution 2018 2018-05 William Czaplyski Author Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Spring 2018 2018 Organic chemistry C–H Functionalization, Photoredox, Polyolefin, Radical, Xanthate eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text William Czaplyski Author Department of Chemistry College of Arts and Sciences Site-Selective Unactivated Aliphatic C–H Functionalization as a Strategy for Molecular Diversification I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. Spring 2018 2018 Organic chemistry C–H Functionalization, Photoredox, Polyolefin, Radical, Xanthate eng Doctor of Philosophy Dissertation Chemistry Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution William Czaplyski Creator Department of Chemistry College of Arts and Sciences I. Strategies for Intermolecular Functionalization of Unactivated Aliphatic C–H Bonds Aliphatic carbon–hydrogen (C–H) bonds are omnipresent in organic compounds, and strategies for their selective functionalization offer unique abilities in organic synthesis. Recent developments in the field of unactivated aliphatic C–H functionalization are described, and the advantages and limitations associated with them are discussed. II. Intermolecular Aliphatic C–H Xanthylation as a Strategy for Small Molecule Diversification The development of a site-selective aliphatic C–H xanthylation using an N- xanthylamide reagent is detailed. The alkyl xanthate products are converted into a wide array of functionality, highlighting the utility as a strategy for two-step C–H diversification. III. C–H Xanthylation as a Strategy for Polyolefin Functionalization and Diversification The application of the previously described aliphatic C–H xanthylation to polyolefins is shown. High levels of polymer functionalization are observed without the need for excess N-xanthylamide reagent, and problematic chain scission does not occur. The strategy is also amenable to the functionalization of high molecular weight commodity polyolefins. IV. Development of an Organic Photoredox-Catalyzed Strategy for Modular Aliphatic C–H Functionalization A modular unactivated aliphatic C–H functionalization strategy using photoredox catalysis is presented. The one-step conversion of C–H to C–N, C–F, C–Br, C–Cl, C–S, and C–C bonds is shown, and mechanistic studies suggest the intermediacy of an oxygen- centered radical. Preliminary results toward polyolefin functionalization are also discussed. V. Quaternary Center Construction via Coupling of Acyl Xanthates with Unactivated Alkenes The construction of quaternary centers from the addition of tertiary acyl xanthates to unactivated olefins is described. A wide variety of functionality is compatible with the transformation, and the subsequent reactivity of alkyl xanthate products allows for the products of net carbodifunctionalization reactions to be accessed. 2018-05 2018 Organic chemistry C–H Functionalization; Photoredox; Polyolefin; Radical; Xanthate eng Doctor of Philosophy Dissertation Erik Alexanian Thesis advisor David Nicewicz Thesis advisor Marcey Waters Thesis advisor Jillian Dempsey Thesis advisor Frank Leibfarth Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Czaplyski_unc_0153D_17809.pdf uuid:2dd24a3c-f64d-455c-b1d2-2bd792c0308f 2020-06-13T00:00:00 2018-04-23T17:47:52Z proquest application/pdf 32638039