Full metadata record
DC FieldValueLanguage
dc.contributorDepartment of Applied Biology and Chemical Technologyen_US
dc.contributor.advisorSo, Chau Ming (ABCT)en_US
dc.creatorNg, Shan Shan-
dc.identifier.urihttps://theses.lib.polyu.edu.hk/handle/200/13650-
dc.languageEnglishen_US
dc.publisherHong Kong Polytechnic Universityen_US
dc.rightsAll rights reserveden_US
dc.titleDevelopment of phosphine ligands for efficient and chemoselective palladium-catalysed cross-coupling reactionsen_US
dcterms.abstractDesign and synthesis of novel phosphine ligands is one of the most enduring and fascinating research areas for chemists. These new designs aim to improve reactions with harsh conditions or achieve challenging goals in transition metal-catalysed reactions. This thesis focuses on the utility of newly synthesised phosphine ligands in Pd-catalysed cross-coupling reactions.en_US
dcterms.abstractFollowing a brief introduction to the development of phosphine ligands utilised in palladium catalysis, Chapter 2 discusses the synthesis of sterically hindered biaryls using an indole-amide-based phosphine ligand in Pd-catalysed Suzuki–Miyaura cross-coupling reactions. This method achieves excellent yields in short reaction times, such as 10 minutes, and with extremely low palladium catalyst loadings down to 50 ppm. As these target compounds serve as the fundamental framework for materials science and pharmaceutical agents, this more efficient, milder, and more diverse synthetic route remains alluring.en_US
dcterms.abstractFrom Chapter 3 onwards, the thesis explores the unconventional and specific chemoselectivity exhibited by a series of C2-alkylated indole-based phosphine ligands in Pd-catalysed borylation. Polyhalogenated aryl triflates, which have multiple reactive sites, were traditionally believed to follow the reactivity order of C–Br > C–OTf > C–Cl. However, this chapter reports a Pd-catalysed chemoselective borylation reaction with a reactivity order of C–Cl > C–OTf. SelectPhos achieves high reactivity and chemoselectivity through a C–H–Pd interaction involving the methine hydrogen of the C2-alkyl group. This interaction may help stabilise the palladium centre and facilitate the activation of the C–Cl bond. Additionally, the catalyst can perform a one-pot two-step sequence of chemoselective borylation followed by intermolecular Suzuki–Miyaura coupling to synthesise asymmetric biaryls containing triflate moieties, paving the way for the synthesis of complicated terphenyls.en_US
dcterms.abstractThe properties of these ligands form the basis for Chapter 4, where 2-alkylated indole-based phosphine ligands are applied to achieve a reactivity order of C–Br > C–Cl > C–OTf in Suzuki–Miyaura cross-coupling reactions with polyhalogenated aryl triflates. Various bromo(hetero)aryl triflates were successfully coupled with (hetero)arylboronic acids, achieving excellent reactivity and chemoselectivity. This catalyst is active at a remarkably low palladium loading of 0.02 mol%. This system demonstrates a sequential dual functionalisation of bromochloroaryl triflates, laying the groundwork for synthesising triphenyl and its derivatives.en_US
dcterms.extentxx, 486 pages : color illustrationsen_US
dcterms.isPartOfPolyU Electronic Thesesen_US
dcterms.issued2025en_US
dcterms.educationalLevelPh.D.en_US
dcterms.educationalLevelAll Doctorateen_US
dcterms.accessRightsopen accessen_US

Files in This Item:
File Description SizeFormat 
8092.pdfFor All Users26.86 MBAdobe PDFView/Open


Copyright Undertaking

As a bona fide Library user, I declare that:

  1. I will abide by the rules and legal ordinances governing copyright regarding the use of the Database.
  2. I will use the Database for the purpose of my research or private study only and not for circulation or further reproduction or any other purpose.
  3. I agree to indemnify and hold the University harmless from and against any loss, damage, cost, liability or expenses arising from copyright infringement or unauthorized usage.

By downloading any item(s) listed above, you acknowledge that you have read and understood the copyright undertaking as stated above, and agree to be bound by all of its terms.

Show simple item record

Please use this identifier to cite or link to this item: https://theses.lib.polyu.edu.hk/handle/200/13650