Show simple item record

dc.contributor.authorRotta-Loria, Nicolas
dc.date.accessioned2017-08-23T18:18:02Z
dc.date.available2017-08-23T18:18:02Z
dc.identifier.urihttp://hdl.handle.net/10222/73156
dc.description.abstractLate-metal catalyzed cross-couplings have emerged as efficient and selective methodologies for the formation of C-C and C-N bonds. The ability to synthesize complex heterocycles from cheap and abundant starting materials is an invaluable asset to the pharmaceutical industry, given that many pharmaceuticals contain at least one heterocyclic component. This reactivity can be achieved by tuning the steric and electronic properties of ancillary ligands to support metal catalysts in the reaction steps leading to the target substrate. The Stradiotto group has developed several state-of-the-art methodologies involving ligands for palladium catalysis, for both C-C and C-N bond-forming reactions. These methodologies can be amalgamated into a multicomponent reaction platform to synthesize more complex products from simple materials. Chapter 1 outlines this concept with the application of a Mor-DalPhos/Pd catalyst in the one-pot synthesis of indoles from acetone and simple amines involving C-C and C-N bond formation. The robust nature of this method can be extended to include benchtop reaction conditions in a one-step, one-pot synthesis of indoles, thus representing a useful synthetic protocol. While palladium provides a powerful tool for C-C and C-N bond formation, the general trend in catalysis has shifted away from the precious metals toward first row metals as economic alternatives. Nickel complexes have recently emerged as excellent catalysts for a number of amination reactions. The ability to utilize ammonia also represents a sought after reaction, due to the widespread availability and synthetic utility of amino-functionalized products. In this regard, Chapter 2 will focus on the development and application of both commercially available and strategically designed ligand classes for the monoarylation of ammonia with substituted heterocycles. Hydrazine represents an important synthon in synthetic chemistry. It is synthesized on multi-ton scale every year and represents an important building block in many industrial processes. Many synthetic challenges arise from using free hydrazine as reactant, which has led to lethargic growth of its application in the field of late-metal catalyzed C-N bond-formation. However, gold-catalyzed methodologies have been developed utilizing NHC ligands to allow for the hydrohydrazination of alkynes with parent hydrazine. Chapter 4 examines the development and application of a series of (PR3)AuCl complexes for use in such transformations, leading to the identification of the first effective phosphine-bound gold complex for use in the hydrohydrazination of alkynes at room temperature.en_US
dc.language.isoenen_US
dc.subjectorganometallicsen_US
dc.subjectlate-metalen_US
dc.subjectpalladiumen_US
dc.subjectnickelen_US
dc.titleAdvances in Late-Metal Carbon-Nitrogen Bond Formation for the Synthesis of Substituted Heterocyclesen_US
dc.date.defence2017-07-19
dc.contributor.departmentDepartment of Chemistryen_US
dc.contributor.degreeDoctor of Philosophyen_US
dc.contributor.external-examinerLaurel Schaferen_US
dc.contributor.graduate-coordinatorMark Stradiottoen_US
dc.contributor.thesis-readerAlison Thompsonen_US
dc.contributor.thesis-readerAlex Speeden_US
dc.contributor.thesis-readerLaura Turculeten_US
dc.contributor.thesis-supervisorMark Stradiottoen_US
dc.contributor.ethics-approvalNot Applicableen_US
dc.contributor.manuscriptsYesen_US
dc.contributor.copyright-releaseYesen_US
 Find Full text

Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record