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Title: Developing Earth-abundant metal-catalysts for hydrofunctionalisation
Author: Paliga, James Francis
ISNI:       0000 0004 7230 5065
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2018
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The iron-catalysed hydromagnesiation of styrene derivatives has been developed further from previous publications, expanding the electrophile scope to enable the regioselective formation of new carbon-carbon and carbon-heteroatom bonds (Scheme A1). A commercially available pre-catalyst and ligand were used to give an operationally simple procedure that did not require prior synthesis of a catalyst. This work also investigated the hydromagnesiation of dienes, using a screen of ligands commonly used in transition metal catalysis. An investigation into the magnesium-catalysed hydroboration of olefins was also carried out. Although mostly unsuccessful, it was demonstrated that in the presence of a magnesium catalyst, a small amount of vinyl boronic ester could be formed from an alkyne (Scheme A2). Simple magnesium salts were also investigated for the reduction of carbonyls. Lastly, this work explored the titanium-catalysed hydrosilylation of olefins, using a novel activation method developed within the group (Scheme A3). The results were compared to those published previously using traditional organometallic activation methods and attempts at identifying conditions to improve chemoselectivity were carried out.
Supervisor: Thomas, Stephen ; Schneider, Uwe Sponsor: Engineering and Physical Sciences Research Council (EPSRC)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: catalysis ; novel reactions ; iron catalyst ; magnesium ; titanium-catalysed reaction