Improved procedures for the glycosylation of serine and threonine utilizing Schiff base activation are reported. The procedures are less expensive and more efficient alternatives to previously published methods. The Schiff bases exhibited ring-chain tautomerism in CDCl₃ as shown by ¹H NMR. Acting as glycosyl acceptors, the Schiff bases reacted at RT with simple sugar peracetate donors with BF₃•OEt₂ promotion to provide the corresponding protected amino acid glycosides in good yields. With microwave irradiation, the reactions were complete in 2-5 minutes. Glycosylation with the dipeptide Schiff base shows the potential of this method in the preparation of peptide building blocks. To investigate this reaction further, direct glycosylation of sugar acetates with FMOC-Ser-OH/OBZl under BF₃•OEt₂ promotion in a microwave provided glycosides in high yield. In addition to the expected glycoside products acetylated side products resulting from acetate migration were isolated, suggesting that activation of the anomeric sugar acetates with a Lewis acid such BF₃•OEt₂ led to an oxocarbenium ion, which rearranged to a 1,2-dioxocarbenium ion because of the acetate participating group at C-2. Solvent participation was also illustrated with acetate migration being more pronounced when CH₃CN was used as a solvent and resulted in less product yield and higher amounts of the acetylated product. The acyl transfer products in these reactions where sugar acetates serve as glycosyl donors is reported for the first time, which also implies that ortho-ester like intermediates are important in the reaction mechanism. Keeping the message segment constant in the sequence H-Tyr-DThr-Gly-Phe-Leu- Ser-CO-NH₂ and modification of the address segment with different carbohydrate moieties had little effect on selectivity for binding at the μ, δ, or κ-opiod receptors. However, substitution of D-threonine with D-serine or the less polar D-alanine in the message segment resulted in a loss of κ-receptor affinity. Further replacement of D-threonine with the more hydrophobic D-valine resulted in complete loss of κ-binding affinity generating pure μ-δ agonists. These data suggests that changes in the message segment of the pharmacophore results in the glycopeptide adopting a conformation that is less favorable for 􀀁-binding receptor activity. Finally, the peripheral administration and i.c.v. tests of the drugs suggest that modifications in the message segment of the pharmacophore influences the potency of these compounds.

This dissertation examines the moralization and beautification campaigns of Mexico City's mayor Ernesto P. Uruchurtu. As head of the Department of the Federal District from 1952-1966, his policies encouraged more popular housing, improved infrastructure, better transportation, cleaner markets, and safer streets. Uruchurtu also aimed to crack down on vice and beautify the city. He believed that through beautification and moralization the city would become safer, healthier, and more livable for all residents. Significantly, he promoted the expansion and improvement of parks, gardens, recreational facilities, the repairing and building of fountains, and the planting of trees and flowers, especially gladiolas. Living with more green and athletic spaces, urban dwellers would have the opportunity to improve physically and spiritually, and would feel inspired to lead more moral lives. Residents could then collectively come together to take pride in their city and generate a stronger sense of civic culture. Consequently, a new generation of youth would grow up in a healthier urban environment and promote national prosperity.This dissertation explores these policies and analyzes the debates surrounding Oscar Lewis's anthropological work, The Children of Sanchez, to highlight anxieties about the effects of urbanization, modernization, and industrialization on the capital's inhabitants. Following the book's publication in 1964, hundreds of articles appeared in newspapers and magazines responding to its subject matter; the intimate details about life for one "typical" poor family living in a slum tenement in the city's center. The debates underscored the uneven benefits of Uruchurtu's policies and offered insights into contradictory depictions of Mexico City: the prospering center of industrialization and growth, and the hub of poverty and despair. Responses to the book expressed how many of the poor experienced economic and political changes during the 1950s and 1960s. The debates also offered details about the cultural and social implications of Uruchurtu's administrative policies and provided a unique opportunity for an open public exchange about life in the capital.

With hundreds of papers published since 2006 on frustrated Lewis pair (FLP) chemistry the development of innovative Lewis acids and Lewis bases is a quickly expanding field. This thesis is separated into two parts. The first part investigates the incorporation of tridentate ligands on ruthenium alkylidene species and their subsequent reactivity with Lewis acids and FLPs in an attempt to synthesize innovative olefin metathesis catalysts. The second part explores the use of ligands coordinated to ruthenium metal centers as a method for expanding the Lewis acid and base functionalities in the field of FLP chemistry. Ruthenium-alkylidene complexes of the general formula ((PEP-Cy)RuX2(CHPh) (E = O, NH, NMe; X = Cl, Br)) were obtained via the reaction of Grubbs 1st generation catalysts with the tridentate ancillary ligands O(CH2CH2PCy2)2 [POP-Cy], HN(CH2CH2PCy2)2 [PN(H)P-Cy] and MeN(CH2CH2PCy2)2 [PN(Me)P-Cy]. Subsequent treatment of GaX3 with these alkylidene species resulted in the formation of cationic alkylidyne-hydride complexes, ([(PEP Cy)Ru(H)(X)(CPh)][GaX4] where E = O, NH, NMe; X = Cl, Br; however, when E = NH, a mixture of alkylidyne-hydride and cationic alkylidene species was observed. Conversely, when E = NMe, alkylidyne-hydride formation was followed by transfer of the alkylidene fragment to the Me of the ligand framework. Subsequently, Ru-acetylide complexes [LRu(PPh3)2CCPh] were reacted with the B(C6F5)3 to afford the para-attacked products [LRu(PPh3)2C=C(Ph)((C6F4)B(F)(C6F5)2)] (L = Cp, Indenyl). Further studies revealed that [IndRu(PPh3)2CCPh] and ER3 (E = B, R = C6F4H; E = Al, R = C6F5) formed FLP mixtures that effected the activation of CO2 between the nucleophilic β-acetylide carbon and the Lewis acid to form [IndRu(PPh3)2C=C(Ph)C(O)O-ER3] or [IndRu(PPh3)2C=C(Ph)C(O ER3)2] when E = Al and R = C6F5. Similarly, these FLP combinations were used to activate phenylacetylene and benzaldehyde forming the species [IndRu(PPh3)2C=C(Ph)C(Ph)=C(H)(ER3)] and [IndRu(PPh3)2C=C(Ph)C(Ph)O-ER3], respectively. Lastly, the synthesis of [((Ph2PC6H4)2BCl)(η6-Ph))RuCl] was achieved via the reaction of (Ph2PC6H4)2BPh with (Ph3P)RuCl2. Subsequent halide abstraction with K[B(C6F5)4] resulted in the formation of [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] which was used as a carbon-based Lewis acid in adduct formation with Lewis bases to yield products of the general form [((Ph2PC6H4)2B)(η5 C6H5 o-LB))RuCl][B(C6F5)4] (LB = PPh3, PCy3, PMe3, SIMes, etc). The activation of H2 was also achieved when combinations of [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] and bulky phosphines were employed, resulting in the products [((Ph2PC6H4)2B)(η5 C6H6))RuCl][B(C6F5)4], [((Ph2PC6H4)2B)(η6 C6H5))RuCl][B(C6F5)4] and [R3PH][B(C6F5)4] (R = Mes, tBu, Cy). Similarly, [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] was used to catalytically hydrogenate sterically encumbered aldimines at room temperature with catalyst loadings as low as 1 mol% via a FLP-type mechanism.

With hundreds of papers published since 2006 on frustrated Lewis pair (FLP) chemistry the development of innovative Lewis acids and Lewis bases is a quickly expanding field. This thesis is separated into two parts. The first part investigates the incorporation of tridentate ligands on ruthenium alkylidene species and their subsequent reactivity with Lewis acids and FLPs in an attempt to synthesize innovative olefin metathesis catalysts. The second part explores the use of ligands coordinated to ruthenium metal centers as a method for expanding the Lewis acid and base functionalities in the field of FLP chemistry. Ruthenium-alkylidene complexes of the general formula ((PEP-Cy)RuX2(CHPh) (E = O, NH, NMe; X = Cl, Br)) were obtained via the reaction of Grubbs 1st generation catalysts with the tridentate ancillary ligands O(CH2CH2PCy2)2 [POP-Cy], HN(CH2CH2PCy2)2 [PN(H)P-Cy] and MeN(CH2CH2PCy2)2 [PN(Me)P-Cy]. Subsequent treatment of GaX3 with these alkylidene species resulted in the formation of cationic alkylidyne-hydride complexes, ([(PEP Cy)Ru(H)(X)(CPh)][GaX4] where E = O, NH, NMe; X = Cl, Br; however, when E = NH, a mixture of alkylidyne-hydride and cationic alkylidene species was observed. Conversely, when E = NMe, alkylidyne-hydride formation was followed by transfer of the alkylidene fragment to the Me of the ligand framework. Subsequently, Ru-acetylide complexes [LRu(PPh3)2CCPh] were reacted with the B(C6F5)3 to afford the para-attacked products [LRu(PPh3)2C=C(Ph)((C6F4)B(F)(C6F5)2)] (L = Cp, Indenyl). Further studies revealed that [IndRu(PPh3)2CCPh] and ER3 (E = B, R = C6F4H; E = Al, R = C6F5) formed FLP mixtures that effected the activation of CO2 between the nucleophilic β-acetylide carbon and the Lewis acid to form [IndRu(PPh3)2C=C(Ph)C(O)O-ER3] or [IndRu(PPh3)2C=C(Ph)C(O ER3)2] when E = Al and R = C6F5. Similarly, these FLP combinations were used to activate phenylacetylene and benzaldehyde forming the species [IndRu(PPh3)2C=C(Ph)C(Ph)=C(H)(ER3)] and [IndRu(PPh3)2C=C(Ph)C(Ph)O-ER3], respectively. Lastly, the synthesis of [((Ph2PC6H4)2BCl)(η6-Ph))RuCl] was achieved via the reaction of (Ph2PC6H4)2BPh with (Ph3P)RuCl2. Subsequent halide abstraction with K[B(C6F5)4] resulted in the formation of [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] which was used as a carbon-based Lewis acid in adduct formation with Lewis bases to yield products of the general form [((Ph2PC6H4)2B)(η5 C6H5 o-LB))RuCl][B(C6F5)4] (LB = PPh3, PCy3, PMe3, SIMes, etc). The activation of H2 was also achieved when combinations of [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] and bulky phosphines were employed, resulting in the products [((Ph2PC6H4)2B)(η5 C6H6))RuCl][B(C6F5)4], [((Ph2PC6H4)2B)(η6 C6H5))RuCl][B(C6F5)4] and [R3PH][B(C6F5)4] (R = Mes, tBu, Cy). Similarly, [((Ph2PC6H4)2B)(η6-Ph))RuCl][B(C6F5)4] was used to catalytically hydrogenate sterically encumbered aldimines at room temperature with catalyst loadings as low as 1 mol% via a FLP-type mechanism.

No description available.

Although C. S. Lewis was not a metaphor theorist, the issue of metaphor appears often enough in his writings for one to cull from them a general theoretical view. This thesis attempts to examine Lewis's thoughts on metaphor against the background of modern metaphor theory. Forty or fifty years ago such a study would have been less fruitful, for his views on metaphor so differed from contemporary theorists that their works offered no positive atmosphere in which to approach his work. Now, however, the general tenor of certain streams in metaphor theory has become more amenable to his views. Indeed, it appears that some key issues raised in modern metaphor theory exist in a seminal form in Lewis's writings. While Lewis cannot be put into any one school, modern theory offers the necessary tools with which to approach his discussions of the figure. This thesis, therefore, begins by briefly outlining the history of metaphor theory in so far as it relates to Lewis. The second chapter discusses his metaphysics, since he believed that his views on metaphor had metaphysical implications. The third and fourth chapters present Lewis's view of metaphor' process and function, as gleaned from his writings. Finally, the thesis concludes by relating Lewis's view back to his metaphysics.

In this thesis, I explore the uses to which children’s authors C.S. Lewis and Philip Pullman put the major biblical theme of the Fall (with passing commentary on Temptation, the precursor to the Fall) in their seminal children’s series The Chronicles of Narnia and the His Dark Materials trilogy. I argue that each author uses the subject of the Fall as a central theme in his series in order to inflect the dominant message of this biblical story (that humanity has fallen from perfection into sin) with their personal opinions on fundamental human questions concerning the nature of God, the difference between good and evil, and the metaphysical ‘rules’ that structure the universe and mankind’s place in it.1 In exploring these issues, I point out the ways in which Pullman and Lewis, in their drastically differing opinions as to the legitimacy of the worldview implicit in the original Bible story, are nevertheless both heavily dependant on the overwhelming influence that the Fall narrative has had on Western culture.

In the history of intercultural relationships, no country has exercised so great an influence on the English geographical imagination as Russia. From its humble beginnings as the kingdom of Muscovy, to the sprawling expanse of the U.S.S.R., Winston Chruchill’s famous “riddle, wrapped in a mystery, inside an enigma” both captivated and repulsed English audiences. Cartographically split between Europe and Asia, the ambiguous nature of Russian culture not only undermined absolute “Orientalist” binaries separating East from West, but also contributed, through the epoch-making fin de siècle influx of Slavic aesthetic forms, to the birth of English modernism. The idea of “Russianess,” for pre-war audiences, proved crucial to unsettling received notions of art, ideology, and identity. This destabilizing effect is especially evident in the work of Wyndham Lewis, T.S. Eliot, and D.H. Lawrence. Despite having largely been dismissed as “reactionary” and “xenophobic” in their political stances, the complex and variegated way in which each author engages with Russia, as this study demonstrates, suggests an underlying ambivalence in their writing. Rather than reflecting a geographic reality, Slavic society, in their hands, appears as a collective fantasy, an external manifestation of their own internal doubts, anxieties, and pre-occupations concerning “Englishness,” which serves to elucidate the conflicted and uncertain politics of twentieth-century avant-garde art.

This thesis is concerned with the use of Lewis base organocatalysts for carboxyl and acyl transfer reactions. Chapter 1 introduces the ability of organic Lewis bases other than DMAP-type to promote a range of asymmetric O-, N- and C-acyl transfer processes. This chapter summarizes the developments in catalyst architectures and approaches to these processes that have been disclosed to date in this dynamic area of asymmetric organocatalysis. Chapter 2 introduces studies into the synthesis of pyrrolyl carbonates via cyclization of gamma-amino esters and ring closing metathesis (RCM) of N-allylamides. The ability of a range of Lewis bases to promote the regioselective O- to C-carboxyl transfer of pyrrolyl carbonates is also presented. Chapter 3 introduces isothiourea DHPB as an efficient Lewis base catalyst for the diastereoselective C-acylation of silyl ketene acetals with anhydrides or benzoyl fluoride, giving 3-acyl-3-aryl or 3-acyl-3-alkylfuranones in excellent yields and stereoselectivities (up to 99:1 dr). Chapter 4 introduces C(2)-aryl substituted DHPB derived-isothioureas as efficient Lewis base catalysts for the enantioselective C-acylation of silyl ketene acetals with propionic anhydride, giving 3-acyl-3-aryl or 3-acyl-3-alkylfuranones in good isolated yields and enantioselectivities (up to 98% ee). This chapter also demonstrates that these chiral isothioureas are required for high reactivity and asymmetry in related acylation manifolds. Chapter 5 presents and overall conclusion for chapters 2,3 and 4. Chapter 6 contains full experimental procedures and characterization data for all compounds synthesized in Chapters 2, 3 and 4.

There is no abstract available for this thesis.