5 research outputs found
Letter to John Butler, Matilda Smith and Lavina Butler from Ira F.M. Butler, Paradine Butler and Rachel Butler
No full textIra F.M. Butler sends his condolences for death of John Butler\u27s wife. He also discusses the birth of another girl, the Frazier River gold mine driving prices up in Oregon, the town of Monmouth growing, and probate issues with Elijah\u27s estate. An August 23, 1858 addendum from Rachael Butler describes family health and wellness. A further addendum from Paradine Butler describes quilting, school and youth activities
C(sp3)-H aminations under first row transition metal catalysis
No full textNitrogen functionality is ubiquitous in biologically active molecules, from naturally occurring alkaloids and peptides to synthetic pharmaceuticals. However, due to its promiscuous reactivity, nitrogen can be challenging to incorporate into molecules and carry through synthetic sequences. Traditional methods to introduce nitrogen (e.g. Mannich, reductive amination) often rely on pre-existing functionality and require additional transformations such as oxidation state changes and/or protecting group maniuplations. C—H amination represents a powerful alternative synthetic strategy. This approach involves the direct functionalization of highly robust sp3 C—H bonds, which allows for the introduction of nitrogen functionality at late stages in synthetic sequences, both obviating the requirement for lengthy functional group manipulation strategies and enabling rapid access to a diversity of structures.
Although small molecule iron and manganese catalysts were first explored for metallonitrene-mediated C—H amination reactions, the majority of synthetic advances in the field have been with noble metal dirhodium carboxylate catalysts. These catalysts are highly reactive and have collectively displayed the ability to efficiently aminate benzylic, ethereal, and aliphatic C—H bonds. However, they are poorly chemoselective in the presence of π-functionality such as olefins and alkynes, and direct addition to these π-bonds is often competitive with desired C—H amination reactivity. It is likely that rhodium’s concerted asynchronous C—H insertion mechanism, which favors functionalization at more electron-rich sites, is responsible for this lack of chemoselectivity. Conversely, first row transition metal catalysts like iron and manganese are thought to react through a stepwise homolytic C—H abstraction/rebound mechanism. We hypothesized that this different mechanism would lead to orthogonal reactivity under first row transition metal catalysis, including the ability to functionalize allylic C—H bonds with high chemoselectivity. In addition, iron and manganese are highly abundant and non-toxic base metals that have been relatively unexplored.
The first chapter of this dissertation describes the development of the first synthetically useful C—H amination method under iron catalysis. This reaction, which employs the bulk commodity complex [FeIIIPc], confirms our initial hypothesis, displaying excellent chemoselectivity (generally >20:1 ins./azir.) for allylic C—H amination over a range of olefin classes and exhibiting site-selectivity trends that are orthogonal to those observed under rhodium catalysis. In addition, this bulky, electrophilic catalyst is able to differentiate between allylic C—H bonds in polyolefinic substrates on the basis of their electronic and steric nature. Mechanistic studies support a stepwise mechanism involving discrete electrophilic intermediates.
In seeking to expand the scope of this C—H amination methodology, we were struck by a clear divergence in the literature between reactivity and selectivity. Existing catalysts for C(sp3)—H amination, including our [FeIIIPc] catalyst, are either highly reactive or highly selective, but not both. We sought to exploit the exquisite chemoselectivity of first row transition metals in order to develop a small molecule C—H amination catalyst that was truly general. The second chapter of this dissertation describes the discovery and development of [Mn(tBuPc)], a novel manganese catalyst that for the first time is able to effectively functionalize all types of sp3 C—H bonds with preparative product yields (>50%) even for very strong 2° and 1° aliphatic C—H bonds, while maintaining excellent chemoselectivity for C—H amination (>20:1) in the presence of readily oxidizable π-bonds. We conduct mechanistic studies to investigate the often drastic reactivity differences between [Mn(tBuPc)] and our previous [FeIIIPc], finding subtle changes in the C—H cleavage step that suggest attenuated radical behavior with manganese relative to iron. The generality of this method and versatility of the oxathiazinane C—H amination product lend it well for application to the diversification of topologically and functionally complex bioactive molecules. This is demonstrated for picrotoxinin and isosteviol derivatives, which maintain (or magnify) the reactivity and selectivity trends observed with the corresponding simple substructural units.Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2017-05-01The student, Shauna Paradine Tschirhart, accepted the attached license on 2015-03-03 at 12:51.The student, Shauna Paradine Tschirhart, submitted this Dissertation for approval on 2015-03-03 at 12:56.This Dissertation was approved for publication on 2015-03-04 at 10:17.DSpace SAF Submission Ingestion Package generated from Vireo submission #7732 on 2015-07-22 at 14:24:08Made available in DSpace on 2015-07-22T22:45:03Z (GMT). No. of bitstreams: 3
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Previous issue date: 2015-03-04Embargo set by: Seth Robbins for item 79955
Lift date: 2017-07-22T22:46:21Z
Reason: Author requested closed access (OA after 2yrs) in Vireo ETD systemLimited Restriction Lifted for Item 79955 on 2017-07-23T09:15:22Z
Frost, Sir David (Paradine), (7 April 1939–31 Aug. 2013), interviewer, author, producer, columnist, and television presenter; Chairman and Chief Executive, David Paradine Ltd, since 1966
No full textPRECISAMOS CONVERSAR SOBRE O ALFRED: A VIOLÊNCIA CONTRA A MULHER NOS FILMES DE HITCHCOCK
No full textA Tese Precisamos conversar sobre o Alfred: a violência contra a mulher nos filmes de Hitchcockpretende investigar a violência contra a mulher como componente estratégico ao suspense hitchcokiano. A filmografia do diretor atravessa cerca de 50 anos do século XX, se iniciando a partir de 1925, com O Inquilino Sinistro (The Lodger), e persistindo, em seus estertores finais, atéTrama Macabra (Family Plot, 1976). Nos filmes de Hitchcock, a audiência é convocada a assumir uma posição pautada por uma dualidade. Num primeiro momento, a audiência simpatiza com as mulheres hitchcoquianas em situações de perigo. Porém, a partir do uso da linguagem cinematográfica, o espectador passa a ser exposto ao pathos das cenas de dor e sofrimento dessas mulheres, o que instabiliza a misoginia que seria de antemão estimulada pela própria narrativa. Temos como operadores conceituais centrais à execução do trabalho os Estudos de Mulheres, com ênfase na Teoria Feminista do Cinema, acionando, para tanto, os trabalhos como os de Judith Butler (1993, 2010, 2010b), Donna Haraway (2004), Julia Kristeva (1988), Tania Modleski (1991, 2005), Laura Mulvey 1996, 2009) e Kaja Silverman (1988). Dentre os filmes de Alfred Hitchcock a serem analisados, encontram-se: Downhill (1927), O Ringue (The Ring, 1927),O Inquilino Sinistro (The Lodger, 1927),Chantagem e Confissão (1929), O Agente Secreto (Secret Agent, 1936), A Estalagem Maldita (Jamaica Inn, 1939), Correspondente Estrangeiro (Foreign Correspondent, 1940),À Sombra de uma Dúvida (Shadow of a Doubt, 1943), Interlúdio (1946), Agonia de Amor (The Paradine Case, 1947), Pacto Sinistro (1951), Disque M para Matar (Dial M for Murder, 1954), Janela Indiscreta (RearWindow, 1954), O Homem Errado (The Wrong Man, 1957), Um Corpo que Cai (Vertigo, 1958), Intriga Internacional (North by Northwest, 1959),Psicose (Psycho, 1960), Os Pássaros (The Birds, 1963), Topázio (Topaz, 1969) eFrenesi (Frenzy, 1972).The Thesis “We need to talk about Alfred: violence against women in Hitchcock’s films” is intended to investigate violence against women as a strategic component to the Hitchcockian suspense. The director's filmography runs through about 50 years of the twentieth century, beginning in 1925 with The Lodger, and persisting in his final rales until Family Plot, 1976. In Hitchcock's films, the audience is called upon to take a dualistic stance. At first, the audience sympathizes with Hitchcockian women in dangerous situations. However, from the use of cinematographic language, the viewer is exposed to the pathos of the scenes of pain and suffering of these women, which destabilizes the misogyny that would have been stimulated by the narrative itself. We have as central conceptual operators to the work of Women's Studies, with emphasis on Feminist Film Theory, triggering, for that, works like those of Judith Butler (1993, 2010, 2010b), Donna Haraway (2004), Julia Kristeva (1988), Tania Modleski (1991, 2005), Laura Mulvey (1996) and Kaja Silverman (1988). Among the Alfred Hitchcock films to be analyzed are Downhill (1927), The Ring (1927), The Lodger (1927), Blackmail (1929), The Secret Agent Agent (1936), Jamaica Inn (1939), Foreign Correspondent, (940), Shadow of a Doubt (1943), Notorious (1946), The Paradine Case (1947), Strangers on a Train (1951), Dial M for Murder (1954), Rear Window (1954), The Wrong Man (1957), Vertigo (1958), Psycho (Psycho, 1960), The Birds (1963), Topaz (1969) and Frenzy (1972).FAPES
The television work of Alfred Hitchcock
No full textThe thesis uses close textual analysis to study and evaluate the television work of Alfred Hitchcock. The corpus consists of the twenty shows personally directed by Hitchcock, including his appearances before and after those shows. In response to most previous writing, which tends to compare the programmes with Hitchcock’s films (often unfairly) the thesis emphasises them as products of television. Programmes are evaluated on the basis of their perceived success as television- if they harness conditions related to television production and integrate them with narrative themes or to create meaning. Hitchcock is considered to be the major creative force in each programme.
Chapter One provides a variety of important contexts including a brief history of US television of the 1950s, key literature on Hitchcock and analyses of contemporaneous programmes not directed by Hitchcock. The textual analysis chapters (2-8) consider aesthetic or thematic programme aspects. Chapter Two studies the various roles played by Hitchcock’s appearances as series host. Chapter Three considers the impact of censorship on programmes frequently dealing with murder, violence and insanity. Chapter Four analyses Hitchcock’s implementation of varieties of voice-over narration, a common device in short dramatic forms. Chapter Five studies Hitchcock’s use of point-of-view shots, particularly in relation to their role in the delivery of the narrative twist. Chapter Six considers the key Hitchcock theme of detachment from the world. Chapter Seven looks at moments from the programmes which demonstrate how aesthetic is influenced by television production conditions.
Hitchcock created a number of television masterpieces. His achievements in television are in many ways comparable in quality and consistency to his theatrical films. Even when considered in the context of other 1950s US anthology dramas, the Hitchcock-directed programmes are superior on many levels. Elements of his film style were highly suited to television production. Many of his greatest achievements embrace and harness television production conditions in their presentation strategies to create an integration of style and meaning
