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Development of an asymmetric NHC-catalyzed cascade reaction and studies towards the asymmetric aminomethylation of enals

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dc.contributor.authorOzboya, Kerem, author
dc.contributor.authorRovis, Tomislav, advisor
dc.contributor.authorHenry, Charles, committee member
dc.contributor.authorMcNally, Andrew, committee member
dc.contributor.authorKennan, Alan, committee member
dc.contributor.authorInamine, Julia, committee member
dc.date.accessioned2015-08-27T03:56:49Z
dc.date.available2015-08-27T03:56:49Z
dc.date.issued2015
dc.description.abstractA cascade reaction is developed to form complex cyclopentanones using an asymmetric Michael/Benzoin sequence. This reaction employs simple aliphatic aldehydes and ketoesters in conjunction with a chiral amine catalyst and a chiral NHC catalyst. Further investigation reveals a surprising interplay between these two catalysts. This relationship is manifested in a pseudo-dynamic kinetic resolution, which is responsible for the high diastereoselectivity observed. Subsequent work details the discovery of the aminomethylation of enals using NHC catalysis. This reaction utilizes an iminium source as well as cinnamaldehyde derivatives to form gamma-amino butyrate derivatives. Rendering this reaction asymmetric has proven a challenge, despite extensive effort to resolve these issues. In the course of these studies, an unexpected NHC-catalyzed Morita-Baylis-Hillman reaction was observed. Optimal conditions for this reaction were established, proving access to useful amino-enals. In an effort to design suitable catalysts for the asymmetric aminomethylation reaction, a strategy for the late-stage manipulation of NHC catalysts was developed. Key to this strategy is the `protection' of the triazolium salt by reduction to the triazoline. An aryl C-Br bond is then exploited for cross-coupling reactions, building a small library of new catalysts. The triazolium salt is then recovered by oxidation with a trityl salt.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierOzboya_colostate_0053A_12817.pdf
dc.identifier.urihttp://hdl.handle.net/10217/166865
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2000-2019
dc.rightsCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.
dc.subjectNHC
dc.subjectorganocatalysis
dc.subjectorganic synthesis
dc.subjectasymmetric catalysis
dc.titleDevelopment of an asymmetric NHC-catalyzed cascade reaction and studies towards the asymmetric aminomethylation of enals
dc.typeText
dcterms.rights.dplaThis Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
thesis.degree.disciplineChemistry
thesis.degree.grantorColorado State University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy (Ph.D.)

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