Arrowsmith, M., 2011. Intramolecular hydroamination of aminoalkenes with group 2 precatalysts: mechanistic insights and ligand design. Thesis (Doctor of Philosophy (PhD)). University of Bath.
Long relegated to the background by the pre-eminence of magnesium-based, stoichiometric Grignard reagents, a distinct chemistry of the heavier alkaline earth metals, calcium, strontium and barium, is only now starting to emerge. As similarities have been drawn between the large, electropositive, redox-inert and d0 alkaline earth Ae2+ dications and the Ln3+ cations of the lanthanide series, a growing group 2-mediated catalytic chemistry has developed over the last decade, including polymerisation reactions, heterofunctionalisation reactions of multiple bonds and some rare examples of dehydrocoupling reactions. Among these catalytic reactions the magnesium- and calcium-catalysed intramolecular hydroamination of aminoalkenes has attracted particular interest. Mechanistic studies have demonstrated many parallels with the lanthanide-mediated catalytic cycle based upon successive σ-bond metathesis and insertion steps. In the first part of this thesis, further investigations into the hydroamination/cyclisation reaction have demonstrated the prominent role of the charge density of the catalytic group 2 cation (M = Mg, Ca, Sr, Ba), the beneficial influence of stabilising spectator ligands, and the importance of the choice of the reactive co-ligand for efficient catalyst initiation. Kinetic analyses of reactions monitored by NMR spectroscopy have given new insight into activation energies, entropic effects, substrate and product inhibition, and kinetic isotope effects, leading to a review of the previously suggested lanthanide-mimetic mechanism. In a second part, this study seeks to address two of the main challenges posed by the intramolecular hydroamination reaction in particular, and heavier alkaline earth-catalysed reactions in general: (i) The need to design new monoanionic spectator ligands capable of stabilising heteroleptic heavier alkaline earth complexes and preventing deleterious Schlenk-type ligand redistribution processes in solution; (ii) The stabilisation of highly reactive heteroleptic group 2 alkyl functionalities for fast, irreversible catalyst initiation and novel reactivity.
|Item Type ||Thesis (Doctor of Philosophy (PhD))|
|Uncontrolled Keywords||catalysis, hydroamination, carbene, dearomatisation, mechanism, ligand design, alkaline earth|
|Departments||Faculty of Science > Chemistry|
|Publisher Statement||UnivBath_PhD_2011_M_Arrowsmith.pdf: © The Author|
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