Palladium-catalysed synthesis of highly functionalised compounds

Phillips, David J. (2018) Palladium-catalysed synthesis of highly functionalised compounds. PhD thesis, University of Glasgow.

Abstract

Palladium-catalysis is extremely important in fine chemical synthesis. This thesis looks at the development of new palladium-catalysed carbon–carbon bond formation reactions, with particular attention to forming new bonds to sp3 carbons.
The opening chapter of this thesis gives an overview of current methods for palladium-catalysed heterocyclisation, and the methods for incorporating further functionalisation into this process, then focuses on the optimisation and expansion of a new palladium-catalysed carboallylation reaction. The reaction mechanism was demonstrated via a deuterium-labelling study, confirming that the reaction proceeds through an isohypsic mechanism.
Chapter 2 begins with a summary of palladium-catalysed isohypsic reactions, and the introduction of the isohypsic–redox sequence. New results are presented on the expansion of this isohypsic–redox sequence to include the oxyallylation–Heck-coupling, and work on the aminoallylation–Grubbs–Wacker oxidation.
Chapter 3 commences with an introduction to MIDA boronates, describing their useful properties along with some uses, particularly in step-wise synthesis. The development of a new palladium-catalysed allylation of MIDA boronates is then detailed. Using MIDA boronates to form a new bond to an sp3 carbon for the first time, this was applicable to a range of allyl halides as well as a large number of MIDA boronates containing a range of functionality. Formation of a new sp3–sp3 carbon–carbon bond was explored, as well as an enantioselective allylation. The application of the allylation was demonstrated in the development of a new palladium-catalysed synthesis of Ibuprofen.
Experimental procedures and data are summarised in Chapter 4. An appendix containing NMR spectra for new compounds is attached.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Palladium-catalysis, isohypsic, MIDA boronates.
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Funder's Name: Engineering and Physical Sciences Research Council (EPSRC), Engineering and Physical Sciences Research Council (EPSRC)
• Supervisor's Name: France, Dr. David J.
• Date of Award: 2018
• Depositing User: Mr David Phillips
• Unique ID: glathesis:2018-9011
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 08 May 2018 09:22
• Last Modified: 18 Jun 2018 12:27
• URI: https://theses.gla.ac.uk/id/eprint/9011