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1	Silver-Mediated Trifluoromethoxylation of Aryl Nucleophiles and Synthesis of 3-Deoxy-3-Fluoromorphine Liang, Theresa 14 November 2012 (has links) Fluorine incorporation has become increasingly important in pharmaceutical applications. Upon fluorination and incorporation of fluorinated moieties such as trifluoromethoxy groups, many small molecules become more bioavailable and metabolically stable and additionally can better cross the blood-brain-barrier. This thesis describes the development of a method mediated by silver salts for the synthesis of pharmaceutical-like trifluoromethoxylated compounds via \(C-OCF_3\) bond formation. Additionally the synthesis of 3-deoxy-3-fluoromorphine via late-stage fluorination of morphine is described as well as in vitro and in vivo evaluation of 3-deoxy-3-fluoromorphine as a potential analgesic. / Chemistry and Chemical Biology antinociception aryl trifluoromethyl ethers cross-coupling fluorinated morphine silver-mediated trifluoromethoxylation chemistry
2	Studies towards Developing Diastereoselective SN1 Reactions of α-Keto Carbocations Dubland, Joshua 06 April 2010 (has links) Although α-keto carbocations have been demonstrated to be viable intermediates in solvolysis reactions, their applications in synthesis are scarce. These species can be considered to be equivalent to “reversed polarity” enolates and, as such, could be useful for the asymmetric formation of carbon-carbon and carbon-heteroatom bonds. In principle, facial selectivity in additions to α-keto carbocations may be induced using easily removed ester, amide, or imide chiral auxiliaries. Efforts to achieve such diastereoselective SN1 reactions of α-keto carbocations are described herein. diastereoselective SN1 reaction alpha-keto carbocation nucleophilic substitution reaction carbon-carbon bond forming reaction carbon-heteroatom bond forming reaction chiral auxiliary asymmetric synthesis Lewis acid-mediated Bronsted acid-mediated silver-mediated organic chemistry leaving group ester amide imide 0490 0485
3	Studies towards Developing Diastereoselective SN1 Reactions of α-Keto Carbocations Dubland, Joshua 06 April 2010 (has links) Although α-keto carbocations have been demonstrated to be viable intermediates in solvolysis reactions, their applications in synthesis are scarce. These species can be considered to be equivalent to “reversed polarity” enolates and, as such, could be useful for the asymmetric formation of carbon-carbon and carbon-heteroatom bonds. In principle, facial selectivity in additions to α-keto carbocations may be induced using easily removed ester, amide, or imide chiral auxiliaries. Efforts to achieve such diastereoselective SN1 reactions of α-keto carbocations are described herein. diastereoselective SN1 reaction alpha-keto carbocation nucleophilic substitution reaction carbon-carbon bond forming reaction carbon-heteroatom bond forming reaction chiral auxiliary asymmetric synthesis Lewis acid-mediated Bronsted acid-mediated silver-mediated organic chemistry leaving group ester amide imide 0490 0485
4	From Copper to Gold: Identification and Characterization of Coinage-Metal Ate Complexes by ESI Mass Spectrometry and Gas-Phase Fragmentation Experiments Weske, Sebastian 30 January 2019 (has links) No description available. 540 coinage metal copper silver gold cuprate argentate aurate ate complex organocuprate organoargentate organoaurate magnesium organocuprate normant cuprate Cu(I) Cu(III) Ag(I) Ag(III) trifluoromethylation copper-mediated trifluoromethylation ruppert prakash c-c coupling cross coupling silver-mediated cross-coupling reactive intermediate reductive elimination counter ion effect esi ms esi-ms gas-phase fragmentation collision-induced dissociation cid gas-phase experiment gas-phase chemistry ion chemistry curiosity driven research Chemie (PPN62138352X)

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