Theses and Dissertations from UMD
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New submissions to the thesis/dissertation collections are added automatically as they are received from the Graduate School. Currently, the Graduate School deposits all theses and dissertations from a given semester after the official graduation date. This means that there may be up to a 4 month delay in the appearance of a give thesis/dissertation in DRUM
More information is available at Theses and Dissertations at University of Maryland Libraries.
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Item Hard-Boiled Anxiety in Hammett, Chandler, and Macdonald(2010) Karydes, Karen Huston; Wyatt, David M.; English Language and Literature; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Between 1946 and 1976 Ross Macdonald produced eighteen Lew Archer novels, the heart of his achievement. The Archer series also extended the work begun by Dashiell Hammett and Raymond Chandler. Together these three writers invented the genre of hard-boiled detective fiction, gave it romantic voice, and used it to increasingly adaptive purposes. For Macdonald, writing his books got him to the far side of pain - to a place where he could make the best of the rest of his life. He had experienced childhood as full of predatory secrets and sexual shame. As soon as he could - and by 1936 both his parents had died - Macdonald reinvented himself and prevailed in this willed performance for twenty years. In 1956, when his own child was in terrible trouble, Macdonald got help for her and, finally, for himself. "Notes of a Son & Father" is the keystone of my project: an unpublished, confessional, harrowing accounting of Macdonald's childhood, marriage, and fatherhood, written for his psychiatrist. I was lucky to find it in the Kenneth and Margaret Millar Papers at the University of California at Irvine Libraries' Special Collections & Archives. A dime-store spiral notebook with 39 pages of small, tightly penciled handwriting: an anguished exercise in courage for Macdonald to write and then give over to readers like me who might come along. In the course of his psychoanalysis, Macdonald began to hope that he could, finally, write about his past in the guise of Freudian fables. In this effort, he extended the hard-boiled genre into emotional territory that Hammett and Chandler anticipated, but never occupied. This new work culminated in the last twelve Archer novels, the best of which are The Galton Case, The Chill, and The Underground Man. In these three works, Macdonald transforms the detective figure into a listener, a man devoted to uncovering not crime but rather the power and logic of archetypal complexes, family romances, folie a deux, the repetition compulsion, and the inversion theory.Item PALLADIUM-CATALYZED ALLYLIC-ARYLATION: MECHANISTIC STUDIES AND APPLICATION TO THE TOTAL SYNTHESIS OF (+/-)-7-DEOXYPANCRATISTATIN DERIVATIVES(2009) Shukla, Krupa; DeShong, Philip; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Palladium-catalyzed carbon-carbon bond formation is one of the most widely used reactions for the synthesis of biologically active substances. The DeShong group has demonstrated that hypervalent silicates can be employed for allyl-aryl carbon-carbon bond couplings in the presence of a Pd(0) catalyst. The goals of this dissertation are (1) to demonstrate application of palladium-catalyzed allylic-arylation coupling to the total synthesis of (+/-)-7-deoxypancratistatin and its analogues, and (2) to study the mechanism of allyl-aryl cross coupling reactions. In spite of the potent antitumor and antiviral activity of (+)-7-deoxypancratistatin, the use of this compound is limited in clinical applications because of its low natural abundance and lack of a practical scalable synthetic route. In order to test the feasibility of siloxane-based coupling in the synthesis of 7-deoxypancratistatin, a simplified analogue of (+/-)-7-deoxypancratistatin was synthesized. The key reaction in the synthesis involved stereoselective construction of a carbon-carbon bond between A and C rings via coupling of an aryl siloxane with an allylic carbonate. While siloxane methodology was successfully applied to the synthesis of a (+/-)-7-deoxypancratistatin analogue, application of this methodology to the natural product (+/-)-7-deoxypancratistatin proved to be a significant challenge. To understand the causes of the failure of the coupling reaction, a detailed mechanistic study was undertaken. Hammett analysis of the allyl-aryl coupling reaction demonstrated that the rate of the coupling reaction was enhanced by electron-withdrawing groups on the aryl siloxane. The positive slope of the Hammett plot indicated a charged transition state in which negative charge on the aryl ring was stabilized inductively. Furthermore, this study provided useful information regarding the nature of ligands on the palladium. Based on this study, a new family of Pd(0) olefin catalysts was developed. These catalysts were found to be highly efficient and formed carbon-carbon bond even at ambient temperature. Novel Pd(0) olefin complexes were successfully employed in the synthesis of (+/-)-7-deoxypancratistatin. The key coupling reaction of allylic carbonate with aryl siloxane produced Hudlicky's intermediate, thus constituting formal total synthesis of the actual product. Though the reaction required higher catalytic loading and proceeded in moderate yields, the ability of the reaction to work at ambient temperature is advantageous for practical synthesis of the natural product. Future studies shall aim at optimization of the key coupling reaction and application of this methodology to the synthesis of pancratistatin and related derivatives.