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Title: Selective oxidation reactions catalysed by Palladium (II)
Author: Dornan, Laura M.
ISNI:       0000 0004 6057 4516
Awarding Body: Queen's University Belfast
Current Institution: Queen's University Belfast
Date of Award: 2016
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Carbonyls are an extremely important class of compounds and have been used in many different industries, including pharmaceuticals, fine chemicals, polymers and bulk commodities. The synthesis of carbonyl compounds through the oxidation of an alcohol or an alkene is an inherently straightforward protocol but despite this, oxidation reactions tend to be avoided industrially. This avoidance can be attributed to the lack of useful and safe methods for oxidation reactions. In this thesis, the oxidation of both alcohols and alkenes to their corresponding carbonyl compounds will be investigated using Pd(ll) catalysis. In Chapter two, the aerobic oxidation of alcohols will be examined using N,O-ligated Pd(ll) complexes. The substrate scope of the reaction will be investigated and methods to increase the turnover number (TON) will be explored. In Chapter three, the use of electron transfer mediators (ETMs) will be examined as a method to increase the TON of aerobic alcohol oxidation. Polyoxometalates will be compared to other traditional ETMs and the applicability of this system to a range of substrates will be studied. In Chapter four, the use of cationic Pd(ll) complexes will be explored for Wacker-type oxidation of terminal alkenes to methyl ketones using hydrogen peroxide. The mechanism of oxidation will be examined through kinetic studies, isotopic labelling and electrospray ionisation spectroscopy.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available