Questa tesi considera tre aspetti di Environmental Regulation. Il primo riguarda i fallimenti del mercato e le azioni correttive corrispondenti del governo. Il secondo prende in esame gli effetti delle politiche di regolamentazione e valuta interventi pubblici efficienti. Il terzo osserva diversità delle normative e indaga le loro interazioni. / This dissertation examines three aspects of incentive problems in Environmental Regulation. The first deals with market failures and the government's corresponding corrective actions. The second examines the effects of regulatory policies and asks which kind of government interventions is efficient. The third observes diversity of regulations and investigates their interactions.

<p>The &#945;-alkylation of ketones is a transformation of central importance to organic synthesis. Our lab recently introduced the N-amino cyclic carbamate (ACC) chiral auxiliaries for asymmetric ketone &#945;-alkylation. ACCs provide significant advantages over existing asymmetric ketone alkylation methods as they are easy to introduce, both deprotonation and alkylation can be run at relatively mild temperatures, stereoselectivity of alkylation is excellent and auxiliary removal is facile. A unique feature of ACCs is their ability to control the regioselectivity of deprotonation through what we have termed Complex Induced Syn-Deprotonation. In what follows, we describe several projects relating to the development and synthetic application of ACCs.</p><p>An optimized synthesis of our most successful ACC auxiliary was developed, including an improved method for the formation of the key N-N hydrazide bond. </p><p>A detailed mechanistic investigation of four ACC auxiliaries was conducted, examining the regio- and stereoselectivity of the alkylations at the level of the ACC hydrazone. This work culminated in a theoretical study of ACC auxiliaries, conducted through a collaboration with the Houk Group at UCLA. </p><p>We also describe the use of ACCs in the development of the first method for the regiocontrolled asymmetric &#945;,&#945;-bisalkylation of ketones. The method proceeds in excellent yield and with >99:1 diastereoselectivity. This method was also extended to the asymmetric &#945;,&#945;,&#945;',&#945;'-tetraalkylation of ketones, enabled by the development of a mild, epimerization-free LDA-mediated isomerization of the &#945;,&#945;-bisalkylated ACC hydrazones.</p><p>Additionally, we discuss three synthetic applications of the ACC &#945;,&#945;-bisalkylation methodology. We report an asymmetric formal synthesis of (+)- and (-)-stigmolone, as well as two approaches to the polyketide fragment of the novel cyclic depsipeptide apratoxin D, which have led to the completion of the first asymmetric total synthesis of apratoxin D.</p> / Dissertation

This thesis described investigations into the synthesis and reactions of chiral monophosphines, in five chapters. Chapter 1 introduces asymmetric catalysis, Chapter 2 and 3 describe the synthesis of enantiomerically pure monophosphine via an oxide and borane route respectively. Chapter 4 describes the organometallic reactions of these monophosphines and Chapter 5 contains experimental details of the reactions. <strong>Chapter 1</strong> describes the importance of chirality and significant asymmetric processes. The literature methods of producing homochiral monophosphines are detailed. <strong>Chapter 2</strong> describes the synthesis of enantiomerically enriched monophosphine oxides. Diastereomerically pure (2R, 4S, 5R)-2-chloro-5-phenyl-3,4-dimethyl-1,3,2-oxazaphospholidine was prepared from PCl₃ and (-)-ephedrine. This compound was reacted with 2-adamantyl magnesium bromide to afford (2R, 4S, 5R) and (2S, 4S, 5R)-3,4-dimethyl-2-2-adamantyl-5-phenyl-1,3,2-oxazaphospholidin-2-oxide after oxidation with ^tBuOOH. An X-ray crystal structure was obtained of the R_P diastereoisomer and a detailed NMR study carried out on the S_P diastereoisomer. The R_P diastereoisomer was reacted with 2-methoxyphenylmagnesium bromide to give R_P-N-methyl-N-(1S,2S)-(1-methyl-2-hydroxy-2-phenyl)-ethyl-P-(2-methoxyphenyl)-P-(2-adamantyl)phosphinamide in 68% yield and 95% d.e. The ephedrinyl residue was replaced by O-methyl under acid catalysis with inversion of configuration and with >85% e.e. Displacement of the methoxy group using phenyl lithium occurred with inversion of configuration to give the corresponding phosphine oxide in 65% e.e., which could be reduced under forcing conditions using polymethylhydrosiloxane in the presence of Ti(OⁱPr)₄. <strong>Chapter 3</strong> describes the synthesis of enantiomerically enriched monophosphines via phosphine borane complexes. Diastereomerically pure (2R, 4S, 5R)-2,5-diphenyl-3,4-dimethyl-1,3,2-oxazaphospholidine borane was prepared directly from PhPCl₂ and (-)-ephedrine, followed by oxidation with BH₃.Me₂S. This compound reacted regiospecifically with ortho-anisyl lithium to afford the product formed by P-O cleavage with >96% d.e. and with retention of configuration at phosphorus. The ephedrinyl residue was replaced by O-methyl under acid conditions with inversion of configuration and with >98% e.e. Ferrocenyl, 1-adamantyl and tert-butyl lithium reagents displaced the methoxy group with inversion of configuration and with >92% e.e., as determined by ¹H NMR methods. The phosphine borane complexes were then reduced quantitatively with Et₂NH with retention of configuration and with >98% e.e. <strong>Chapter 4</strong> describes the synthesis of indium and rhodium complexes of (S)-t-butyl-(2-methoxyphenyl)-phenyl phosphine and (S)-ferrocenyl-(2-methoxyphenyl)-phenyl phosphine. The iridium complexes are shown to reduce a range of prochiral olefins, including Z-methyl-2-acetylamino-3-phenylpropenoate (MAC) in up to 19% e.e. The di-(R,R)-(ferrocenyl-(2-methoxyphenyl)-phenyl phosphine) rhodium complex is more selective, reducing MAC in 54% e.e., while the rhodium complex of (S)-t-butyl-(2-methoxyphenyl)-phenyl phosphine reduces MAC in 24% e.e.

Rhodium-catalyzed hydroacylation is a powerful and atom-economical method for synthesizing ketones from aldehydes and olefins. Despite this, a narrow scope of reactive substrates has limited the utility and broad application of this transformation. Efforts towards the development of new classes of reactive substrates have focused on the use of oxygen- and sulfur-containing olefins, which have enabled various modes of reactivity and thus allowed access to novel types of hydroacylation products. In addition to reactivity, a key to the success of these transformations is the control of regio-, stereo-, and chemoselectivity. In combination with substrate structure, strategies in enantioselective catalysis and metal-organic cooperative catalysis have been applied to achieve requisite reactivity and selectivity when required. A variety of products, such as medium-sized heterocycles, branched sulfur-containing and β-hydroxy ketones, and ketones bearing quaternary carbon centres have been synthesized via hydroacylation using these strategies. A method for preparing polyelectrolyte-stabilized palladium nanoparticles and their use in Suzuki coupling reactions have also been developed.

Rhodium-catalyzed hydroacylation is a powerful and atom-economical method for synthesizing ketones from aldehydes and olefins. Despite this, a narrow scope of reactive substrates has limited the utility and broad application of this transformation. Efforts towards the development of new classes of reactive substrates have focused on the use of oxygen- and sulfur-containing olefins, which have enabled various modes of reactivity and thus allowed access to novel types of hydroacylation products. In addition to reactivity, a key to the success of these transformations is the control of regio-, stereo-, and chemoselectivity. In combination with substrate structure, strategies in enantioselective catalysis and metal-organic cooperative catalysis have been applied to achieve requisite reactivity and selectivity when required. A variety of products, such as medium-sized heterocycles, branched sulfur-containing and β-hydroxy ketones, and ketones bearing quaternary carbon centres have been synthesized via hydroacylation using these strategies. A method for preparing polyelectrolyte-stabilized palladium nanoparticles and their use in Suzuki coupling reactions have also been developed.

Bibliography: leaves 159-164. / iv, 158 leaves ; 30cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis examines routes for the asymmetric synthesis of three members of the nonsteroidal anti-inflammatory class of drugs (NSAIDs) The aryl propanoic acid ibuprofen is synthesized in 96% e.e. Control of stereochemistry is achieved by use of the Sharpless epoxidation reaction, followed by reduction of the product epoxide by complex hydride with assistance by titanium tetraisopropoxide acting as a Lewis acid. The final step is the coupling of an optically active carboxylic acid intermediate with the iso-butyl side chain to give (S)-ibuprofen. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1997?

Bibliography : leaves 198-204. / vi, 204 leaves ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1992

All venture capital investments exhibit some form of asymmetric information. The seminal paper on the structure of venture investments, Kaplan and Stromberg (2004), investigates how venture capitalists use deal construction to control agency conflicts within funded deals and their associated internal, external and execution risks. Another key strand of the academic literature has reviewed the contractual arrangements venture capital firms reach, the process of venture capital selection and determinants of their success from a post-investment perspective (Fried and Hisrich (1994), Manigart, Vermeir and Sapienza (1996), Gompers and Lerner (2004), Wright and Robbie (1998)). This thesis also explores venture capital investment, albeit from a preinvestment standpoint. In contrast to Kaplan and Stromberg???s (2004) demonstration of the use of venture capital mechanisms to control agency issues, this research addresses how agency issues influence the final selection of potential investments by venture capitalists. Kaplan and Stromberg (2004) use post-funding metrics to capture risks, which influence post-contract design. From a pre-funding perspective, internal, external and execution risks are subjective, rare and difficult to measure. Nevertheless, this thesis uses pre-funding proxies to replicate these risks, some of which have direct empirical academic support. Information for sixtytwo deals, thirty-four funded and twenty-eight unfunded, was hand collected through a combination of surveys, interviews and consultation with five of Australia???s leading venture capital firms, and individuals from the Australian Private Equity and Venture Capital Association (AVCAL) board and executive. The key results indicate that once past initial screening stages, investment proposals that have a higher likelihood of receiving venture investment are those that had prior government investment, and/or, where the entrepreneur has proposed the investment be through milestone tranches and where revenue is already being generated (for early stage ventures). The results suggest that venture capitalists tend to allocate capital to investments perceived as ???safer??? with respect to agency conflicts. More specifically, venture capitalists are more reliant on signals of quality and lower risk, such as government grants, restriction of capital outlay and prior revenue generation ??? all of which reduce associated levels of internal and execution risk in new ventures.

Thesis (S.M.)--Massachusetts Institute of Technology, 2007. / Title from title screen (viewed Apr. 16, 2008). "June 2007." Includes bibliographical references (p. 137-138). Also issued in paper format.

Thesis (M.A.)--Bowling Green State University, 2008. / Document formatted into pages; contains vi, 117 p. Includes bibliographical references.