MECHANISMS AND RATIONAL CATALYST DESIGN OF ORGANIC TRANSFORMATIONS FOR THE SYNTHESIS OF NEW C-C AND C-X BONDS

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dc.contributor.advisorGutierrez, Osvaldoen_US
dc.contributor.authorRotella, Madeline Elizabethen_US
dc.contributor.departmentChemistryen_US
dc.contributor.publisherDigital Repository at the University of Marylanden_US
dc.contributor.publisherUniversity of Maryland (College Park, Md.)en_US
dc.date.accessioned2022-02-02T06:38:04Z
dc.date.available2022-02-02T06:38:04Z
dc.date.issued2021en_US
dc.description.abstractThe creation of new C-C or C-X bonds, where X can be oxygen, nitrogen or fluorine, is vital to organic synthesis and the discovery of new methods for complex molecule synthesis. In many cases, the mechanism of these transformations is not investigated, although an understanding of the underlying mechanism would allow for rational design of new catalysts and would lead to the development of novel reactivity. Computational studies probing the mechanisms of valuable synthetic methods including C-H oxidation, organocatalysis, nickel photocatalysis, alkyne metathesis and multicomponent reactions are presented. Specifically, computational methods were used in the development of a novel tetradentate amine iron (II) catalyst for the promotion of C(sp3)-H oxidation (Chapter 1). Next, the mechanism of an organocatalyzed amination was studied thoroughly with density functional theory (DFT) calculations in combination with molecular dynamics simulations to develop a predictive model for reactivity for use in the creation of new catalysts in the field of amination chemistry (Chapter 2). Additionally, the mechanism of a regio- and enantioselective iridium-catalyzed asymmetric fluorination was studied, with an emphasis on determining the role of the trichloroacetimidate group in the reaction (Chapter 3). Further, the mechanisms of various transition metal-catalyzed C-C bond formations were studied through computationally. First, a photoredox/nickel-dual catalyzed Tsuji-Trost reaction was studied through DFT and DLPNO-CCSD(T) calculations to investigate the stereoselectivity of the reaction as well as the order of reaction events. Next, a photoredox/nickel-dual catalyzed C-C bond formation using oxanorbornadienes as electrophilic coupling partners was investigated computationally (Chapter 4). Additionally, the mechanism of tungsten- and molybdenum-catalyzed alkyne metathesis as well as the difference in reactivity between the two metals was explored (Chapter 5). A nickel-catalyzed diarylation of alkenes was studied computationally, with particular emphasis on the role of the phosphine ligand in controlling regioselectivity (Chapter 6). Finally, an iron-catalyzed dicarbofunctionalization of vinyl ethers with aryl Grignard reagents and alkyl halides or (fluoro)alkyl halides was developed experimentally (Chapter 7).en_US
dc.identifierhttps://doi.org/10.13016/jwpe-wl5c
dc.identifier.urihttp://hdl.handle.net/1903/28367
dc.language.isoenen_US
dc.subject.pqcontrolledOrganic chemistryen_US
dc.subject.pquncontrolledcomputational chemistryen_US
dc.subject.pquncontrolleddensity functional theoryen_US
dc.subject.pquncontrollediron catalysisen_US
dc.subject.pquncontrolledmechanistic studiesen_US
dc.subject.pquncontrolledorganocatalysisen_US
dc.subject.pquncontrolledtransition metal catalysisen_US
dc.titleMECHANISMS AND RATIONAL CATALYST DESIGN OF ORGANIC TRANSFORMATIONS FOR THE SYNTHESIS OF NEW C-C AND C-X BONDSen_US
dc.typeDissertationen_US

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