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dc.contributor.authorBurnie, Andrew
dc.contributor.otherQueen's University (Kingston, Ont.). Theses (Queen's University (Kingston, Ont.))en
dc.date.accessioned2018-09-05T21:18:35Z
dc.date.available2018-09-05T21:18:35Z
dc.identifier.urihttp://hdl.handle.net/1974/24502
dc.description.abstractTransition metal-catalyzed higher-order carbocyclization reactions provide a versatile and atom-economical approach to the construction of carbo- and heterocyclic ring systems. The ability to efficiently assemble complex and often functionalized (poly)cyclic molecules from relatively simple starting materials in a highly regio-, diastereo- and/or enantioselective manner, depending on the substrate(s) and metal catalyst employed, provides an attractive method for target-directed synthesis. In this regard, rhodium-catalyzed cyclocarbonylation reactions afford a convenient route to the synthesis of various cyclic ketone derivatives, and the utility of these transformations is emphasized by the number of natural product syntheses incorporating this transformation as a key ring-forming step. The following thesis is divided into three key chapters, encompassing a literature review followed by two research chapters, further divided according to the type of transformation discussed. Chapter 1 commences with an overview of transition metal-catalyzed higher order carbocyclization reactions and an introduction to the Pauson–Khand reaction, which is followed by a detailed account of various rhodium-catalyzed semi-intermolecular [(m+n)+1] cyclocarbonylation processes. The final section in this chapter presents the application of rhodium-catalyzed cyclocarbonylation reactions to the total synthesis of several complex natural products. Chapter 2 describes the development of the rhodium-catalyzed [(3+2)+1] carbocyclization reaction of alkylidenecyclopropane (ACP) derivatives with carbon monoxide (CO). Following a brief introduction on the chemistry of three-carbon components in metal-catalyzed carbocyclization processes, our work on the carbocyclization reaction of ACPs with CO for the construction of bicyclic phenols will be presented. The last section in Chapter 2 will discuss the development of the cyclocarbonylation reaction of ACPs containing tetrasubstituted olefins with CO to provide bicyclohexa-2,5-dienones. Chapter 3 begins with an introduction to the enantioselective Pauson–Khand-type (PK-type) reaction of various 1,6-enyne derivatives with CO. The remainder of Chapter 3 is given to the discussion of our efforts towards the enantioselective rhodium-catalyzed PK-type reaction of 1,6-chloroenynes containing trisubstituted olefins for the preparation of bicyclopentenones containing vicinal quaternary and tertiary stereogenic centers. The preliminary scope and some of the limitations of this process will be outlined.en_US
dc.language.isoenen_US
dc.relation.ispartofseriesCanadian thesesen
dc.rightsQueen's University's Thesis/Dissertation Non-Exclusive License for Deposit to QSpace and Library and Archives Canada*
dc.rightsProQuest PhD and Master's Theses International Dissemination Agreement*
dc.rightsIntellectual Property Guidelines at Queen's University*
dc.rightsCopying and Preserving Your Thesis*
dc.rightsThis publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.*
dc.subjectRhodiumen_US
dc.subjectCyclocarbonylationen_US
dc.subjectCarbocyclizationen_US
dc.subjectPauson–Khanden_US
dc.titleRhodium-Catalyzed Cyclocarbonylation Reactions: Construction of Unsaturated Six-Membered Rings and Enantioselective Pauson–Khand-Type Reactions of 1,6-Chloroenynesen_US
dc.typethesisen
dc.description.degreeDoctor of Philosophyen_US
dc.contributor.supervisorEvans, P. Andrew
dc.contributor.departmentChemistryen_US
dc.embargo.termsTo protect unpublished work from copetitorsen_US
dc.embargo.liftdate2023-09-05T16:04:28Z


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