ingest cdrApp 2018-06-13T17:35:55.800Z 51cd2fe2-3fd7-401f-a923-a97bc3db68a2 modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T18:12:20.751Z Setting exclusive relation addDatastream MD_TECHNICAL fedoraAdmin 2018-06-13T18:12:32.654Z Adding technical metadata derived by FITS addDatastream MD_FULL_TEXT fedoraAdmin 2018-06-13T18:12:48.072Z Adding full text metadata extracted by Apache Tika modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T18:12:48.898Z Setting exclusive relation modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-11T18:38:23.937Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-18T13:53:36.674Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-08-21T22:47:19.188Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-09-28T14:19:28.371Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-12T14:06:17.418Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-17T19:28:21.313Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2019-03-22T17:17:36.264Z Desiree Matias Author Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Spring 2018 2018 Organic chemistry Inorganic chemistry Aziridination, Benzene Oxide, Carbodicarbenes, Diimide, Hydroarylation, Hydroxylamine eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text Desiree Matias Author Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Spring 2018 2018 Organic chemistry Inorganic chemistry Aziridination, Benzene Oxide, Carbodicarbenes, Diimide, Hydroarylation, Hydroxylamine eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text Desiree Matias Author Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Spring 2018 2018 Organic chemistry Inorganic chemistry Aziridination, Benzene Oxide, Carbodicarbenes, Diimide, Hydroarylation, Hydroxylamine eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text Desiree Matias Author Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Spring 2018 2018 Organic chemistry Inorganic chemistry Aziridination, Benzene Oxide, Carbodicarbenes, Diimide, Hydroarylation, Hydroxylamine eng Doctor of Philosophy Dissertation Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael T. Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Desiree Matias Creator Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Organic chemistry Inorganic chemistry Aziridination; Benzene Oxide; Carbodicarbenes; Diimide; Hydroarylation; Hydroxylamine eng Doctor of Philosophy Dissertation Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael T. Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution 2018 2018-05 Desiree Matias Author Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Spring 2018 2018 Organic chemistry Inorganic chemistry Aziridination, Benzene Oxide, Carbodicarbenes, Diimide, Hydroarylation, Hydroxylamine eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael T. Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text Desiree Matias Author Department of Chemistry College of Arts and Sciences Activation of Carbodicarbene Catalysts for Diene Hydrofunctionalization and Exploration of Chemical Reactivity Using Commodity Chemicals I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. Spring 2018 2018 Organic chemistry Inorganic chemistry Aziridination, Benzene Oxide, Carbodicarbenes, Diimide, Hydroarylation, Hydroxylamine eng Doctor of Philosophy Dissertation Chemistry Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael T. Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Desiree Matias Creator Department of Chemistry College of Arts and Sciences I. Lewis Acid Activation of Carbodicarbene Catalysts for Rh-Catalyzed Hydroarylation of Dienes The activation of carbodicarbene (CDC)−Rh(I) pincer complexes by secondary binding of metal salts is reported for the catalytic site-selective hydroarylation of 1,3-dienes. The reactions are promoted by 5 mol % of a readily available tridentate (CDC)−Rh complex in the presence of an inexpensive lithium salt. A variety of terminal and internal dienes were tolerated under the reaction conditions, as well as ester, alkyl halide, and boronate ester functional groups. X-ray crystallographic data and mechanistic experiments provide support for the role of the metal salts on catalyst activation and shed light on the reaction mechanism. The increased efficiency (120 to 22 °C) made available by catalytic amounts of metal salts to catalysts containing C(0) donors is a significant aspect of the disclosed studies. II. Synthesis and Desymmetrization of Fully Substituted, Meso-Fused Systems Derived from Benzene Oxide Ozonolysis of the Diels–Alder adducts derived from benzene oxides and N-alkylmaleimides resulted in fully-substituted, meso-bicyclic systems bearing six contiguous stereocenters, isolated as diols upon reductive workup with NaBH4. Variation in the workup allowed for isolation of two different diastereomers, through double epimerization of the imide stereocenters. Detailed study of each component of the workup revealed that the unexpected diastereomer arose from epimerization of the product through the action of in situ-generated base, rather than a retro-Diels–Alder/recombination sequence during the ozonolysis. These meso-diols were transformed in high yields to enantioenriched desymmetrized products via asymmetric nucleophilic epoxide opening and acylation reactions, providing a strategy for obtaining highly-substituted, enantioenriched fused rings through desymmetrization. III. Hydroxylamine as a Precursor for Nitrene and Diimide Formation: C−C Bond Aziridination and Reduction Hydroxylamine is used as a precursor for metal-nitrenoids and diimide. The first part of this chapter covers the initial discovery that hydroxylamine can be used for the aziridination of alkenes in the presence of CO2, a protecting group, and a rhodium catalyst. The reactivity remains unoptimized, despite significant efforts. During these studies, the reduction of alkenes under similar conditions was observed. The second part of this chapter discusses the in situ formation of diimide with the use of hydroxylamine and a protecting group. An initial substrate scope is presented, although some challenges remain. Terminal olefins are reduced in high yields, whereas internal olefins are less reactive. The reduction of terminal alkynes is also possible, albeit in lower yields. Further studies should reveal the mechanism of the reaction and should provide optimize conditions for the less reactive substrates. 2018-05 2018 Organic chemistry Inorganic chemistry Aziridination; Benzene Oxide; Carbodicarbenes; Diimide; Hydroarylation; Hydroxylamine eng Doctor of Philosophy Dissertation Jeffrey Johnson Thesis advisor David Nicewicz Thesis advisor Michael T. Crimmins Thesis advisor Michel Gagne Thesis advisor Alexander Miller Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Matias_unc_0153D_17537.pdf uuid:939d5922-38aa-4306-a90f-65d810168ea2 2020-06-13T00:00:00 2018-05-10T00:10:32Z proquest application/pdf 3690308