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Synthesis of Enantioenriched 1,5-Dienes and 1,5-Enynes by a Palladium-Catalyzed 3,3'-Reductive Elimination: Methodology Development and Mechanistic StudiesArdolino, Michael Joseph January 2014 (has links)
Thesis advisor: James P. Morken / This dissertation details the development, application and study of new palladium-catalyzed carbon-carbon bond forming strategies that generate synthetically useful enantioenriched small molecules. Controlled by a bidentate phosphine ligand, these transformations are thought to operate through a unique 3,3'-reductive elimination that leads to high regio- and stereoselectivity. Specifically, Chapter 1 introduces background on prior work that led to the first allyl-allyl coupling to deliver branched 1,5-dienes, and presents new computational studies on the origins of regioselectivity with mono- and bidentate ligands. Building on these studies, Chapter 2 describes the development of a diastereoselective allyl-allyl coupling of substituted allylboron reagents with allylic chloride electrophiles. To extend the scope of allyl-allyl coupling, Chapter 3 details further reaction optimization and mechanistic studies that have allowed for increasingly congested bond formations. In Chapter 4, a related allyl-propargyl coupling to give enantioenriched 1,5-enynes through stereospecific reactions and kinetic resolution is presented. These developments are accompanied by laboratory and computational data that provide a deeper understanding of reaction mechanisms and the origins of regio- and stereoselectivity. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
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Exploring new gold-catalyzed cyclization reactions of 1,5-enynes and development of an intermolecular phenol synthesisHuguet i Subiela, Núria 08 March 2013 (has links)
Las sales de oro se han convertido en uno de los catalizadores por excelencia en una gran
variedad de transformaciones orgánicas mediante la activación selectiva de alquinos, alenos y
alquenos. Parte del trabajo de esta tesis doctoral se ha centrado en el estudio de la naturaleza
carbénica o carbocatiónica de los intermedios de reacción presentes en las
cicloisomerizaciones de 1,5-eninos catalizadas por complejos de oro. De esta forma se han
desarrollado distintas metodologías de ciclación dando lugar a diferentes productos tricíclicos
a partir de oxo-1,5-eninos o 1,5-bencileninos. Además, se ha podido aplicar estas nuevas
metodologías de ciclación en la síntesis de productos naturales como etapa clave de la misma.
Por último, nuestro interés se ha centrado en el desarrollo de reacciones intermoleculares de
gran utilizad química catalizadas por oro. Por ello hemos desarrollado la síntesis de fenoles
substituidos a partir de diferentes acetilenos y furanos. / Gold salts and complexes are the most active catalysts for the activation of alkynes, allenes and
alkenes. Part of this Doctoral Thesis is focused on the study of the carbenic or cationic character
of the reaction intermediates presents in the cycloisomerizations of 1,5-enynes catalyzed by goldcomplexes.
Different methodologies have been developed to synthesize different tryciclic
products from oxo-1,5-enynes or 1,5-benzylenynes. Moreover, these methodologies were applied
successfully as the key step in the synthesis of natural products. Finally, our interest was focused
on the development of intermolecular gold-catalyzed reactions. Therefore, we have developed a
general synthesis of trisubstituted phenols from alkynes and furans.
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