dc.contributor.advisor | Montchamp, Jean-Luc | |
dc.contributor.author | Bravo-Altamirano, Karla | en_US |
dc.date.accessioned | 2014-07-22T18:46:54Z | |
dc.date.available | 2014-07-22T18:46:54Z | |
dc.date.created | 2007 | en_US |
dc.date.issued | 2007 | en_US |
dc.identifier | etd-04252007-115357 | en_US |
dc.identifier | cat-001315425 | en_US |
dc.identifier.uri | https://repository.tcu.edu/handle/116099117/3967 | |
dc.description.abstract | The work developed in this dissertation consists in the development of new methodologies for the preparation of H-phosphinic acid derivatives and their P-chiral counterparts. Special emphasis is given to the role of H-phosphinates as useful synthons for organophosphorus compounds via tandem processes. A review of the most relevant literature in terms of the preparation methodologies and reactivity of H-phosphinic acid derivatives is provided in Chapter I. The following chapter describes the addition of hypophosphorous compounds to unsaturated substrates in presence of metal-catalysts. The mechanism, regioselectivity on alkynes, and reactivity of substituted alkenes, allenes, allenols, and 1,3-dienes as substrates in a palladium-catalyzed hydrophosphinylation was investigated. A novel alkyne hydrophosphinylation catalyzed by nickel chloride or its hydrate in the absence of added ligand was discovered and exploited in the synthesis of various important organophosphorus compounds.^The third chapter details a tandem esterification - cross-coupling reaction of alkyl phosphinates with aryl, heteroaryl, alkenyl, and benzylic halides and triflates. Thus the reaction of the electrophilic substrate with a hypophosphorous acid salt, in the presence of a silicate, a base and the palladium catalyst provided directly a wide variety of H-phosphinates, which were not accessible previously.In the following chapter, transition metal-catalyzed reactions of hypophosphorous compounds with allylic electrophiles are disclosed. Allylic acetates, benzoates and carbonates undergo an effective cross-coupling in the presence of palladium catalysts where pure H-phosphinic acids can be isolated by a simple acidic work-up or esterified in situ to the corresponding H-phosphinate esters. Chapter V describes a palladium-catalyzed dehydrative allylation of hypophosphorous acid with allylic alcohols, in the absence of additives.^The next chapter focuses on P-H bond activation of H-phosphinates through catalytic allylation and oxidation strategies, which lead to disubstituted phosphinic acid and phosphonic acids, respectively. In the last chapter, desymmetrization strategies to access P-chiral H-phosphinates are reported. Two different avenues are explored: the use of chiral ligands in palladium-catalyzed reactions and the use of chiral auxiliaries by means of esterification of hypophosphorous acid with chiral alcohols, where 8-phenylmenthol provides, in a palladium-catalyzed hydrophosphinylation reaction, our best result with around 70% diastereomeric excess. | |
dc.format.medium | Format: Online | en_US |
dc.language.iso | eng | en_US |
dc.publisher | Fort Worth, Tex. : Texas Christian University, | en_US |
dc.relation.ispartof | Texas Christian University dissertation | en_US |
dc.relation.ispartof | UMI thesis. | en_US |
dc.relation.requires | Mode of access: World Wide Web. | en_US |
dc.relation.requires | System requirements: Adobe Acrobat reader. | en_US |
dc.subject.lcsh | Organophosphorus compounds. | en_US |
dc.title | New methodologies for the preparation of organophosphorus compounds via carbon-phosphorus bond formation | en_US |
dc.type | Text | en_US |
etd.degree.department | Department of Chemistry | |
etd.degree.level | Doctoral | |
local.college | College of Science and Engineering | |
local.department | Chemistry and Biochemistry | |
local.academicunit | Department of Chemistry and Biochemistry | |
dc.type.genre | Dissertation | |
local.subjectarea | Chemistry and Biochemistry | |
etd.degree.name | Doctor of Philosophy | |
etd.degree.grantor | Texas Christian University | |